Electroluminescent Device

ABSTRACT

Disclosed are electroluminescent devices that comprise organic layers that contain dibenzofuran compounds. The compounds are suitable components of, for example, blue-emitting, durable, organo-electroluminescent layers. The electroluminescent devices may be employed for full color display panels in, for example, mobile phones, televisions and personal computer screens.

The present invention relates to electroluminescent devices thatcomprise organic layers that contain dibenzofuran compounds. Thecompounds are suitable components of, for example, blue-emitting,durable, organo-electroluminescent layers. The electroluminescentdevices may be employed for full color display panels in, for example,mobile phones, televisions and personal computer screens.

H. O. Wirth et al., Die Makromolekulare Chemie 86 (1965) 139-167describes the synthesis and properties of oxydo-p-oligophenylenes. Thefollowing two dibenzofuran compounds are described therein:

JP9151182 discloses dibenzofurandiamine derivatives, which are suitableas a positive hole transporting agent, etc., in electrophotographicphotoreceptor, solar cell, electroluminescence element etc. Thedibenzofurandiamine derivatives are represented by the following formula

wherein R₁ to R₅ are each a halogen, a (substituted)alkyl, a(substituted)alkoxy, a (substituted)aryl or (substituted)aralkyl; (a),(b), (c) and (d) are each 0-5; (e) is 0-6. The following compounds areexplicitly disclosed in JP9151182:

JP2004311404 discloses compounds having at least one biaryl partstructure for use in OLED application. The dimeric dibenzofuran compoundshown below is explicitly mentioned.

WO03105538 relates to benzotriazole compounds and their use in OLEDapplication. The dimeric benzotriazole compound shown below isexplicitly mentioned.

The compounds shown below are also known:

Surprisingly, it was found that luminescent devices, which are highdurability besides high in the efficiency of electrical energyutilisation and high in luminance, can be obtained if specificbenzofuran compounds are used, especially as light emitting substances.

Accordingly, the present invention relates to compounds of the formula

wherein R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸, R⁹¹, R⁹², R⁹³, R⁹⁴, R⁹⁵,R⁹⁶, R⁹⁷, R^(91′), R^(92′), R^(93′), R^(94′), R^(95′), R^(96′) andR^(97′) are independently of each other H, —OR²⁰¹, —SR²⁰² and/or—NR²⁰³R²⁰⁴, C₁-C₂₄alkyl; C₁-C₂₄alkyl, which is substituted by E and/orinterrupted by D; C₂-C₁₈alkenyl, C₂-C₁₈alkenyl, which is substituted byE, C₃-C₈cycloalkyl, C₃-C₈cycloalkyl, which is substituted by G, aryl,aryl, which is substituted by G, heteroaryl, or heteroaryl, which issubstituted by G, silyl,

SiR⁶²R⁶³R⁶⁴, —CN, cyclic ether, —B(OR⁶⁵)₂ and/or halogen, especiallyfluorine, orR⁸¹ and R⁸², R⁸² and R⁸³, R⁸³ and R⁸⁴, R⁸⁵ and R⁸⁶, R⁸⁶ and R⁸⁷, R⁸⁷ andR⁸⁸, R⁹⁷ and R⁹⁶, R⁹⁶ and R⁹⁵, R⁹⁵ and R⁹⁴, R^(97′) and R^(96′), R^(96′)and R^(95′), R^(95′) and/or R^(94′), and/or two of the groups R⁹¹, R⁹²and R⁹³ or R^(91′), R^(92′) and R⁹³, which are in neighbourhood to eachother, together form a group

wherein A⁴¹, A⁴², A⁴³, A⁴⁴, A⁴⁵, A⁴⁶ and A⁴⁷ are independently of eachother H, halogen, hydroxy, C₁-C₂₄alkyl, C₁-C₂₄alkyl which is substitutedby E and/or interrupted by D, C₁-C₂₄ perfluoroalkyl, C₅-C₁₂cycloalkyl,C₅-C₁₂cycloalkyl which is substituted by G and/or interrupted by S—,—O—, or —NR⁵—, C₅-C₁₂cycloalkoxy, C₅-C₁₂Cycloalkoxy which is substitutedby E, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G.C₂-C₂₄alkenyl, C₂-C₂₄alkynyl, C₁-C₂₄alkoxy, C₁-C₂₄alkoxy which issubstituted by E and/or interrupted by D, C₇-C₂₅aralkyl, C₇-C₂₅aralkyl,which is substituted by G, C₇-C₂₅aralkoxy, C₇-C₂₅aralkoxy which issubstituted by E, or —CO—R⁸,M is a bonding group, such as a single (direct) bond, —CO—, —COO—; —S—;—SO—; —SO₂—; —O—; C₁-C₁₂alkylene, C₂-C₁₂alkenylene, or C₂-C₁₂alkinylene,which are optionally interrupted by one or more —O—, or —S—; or a group[M¹]_(n), wherein n is an integer 1 to 20, M¹ is arylene, orheteroarylene, which is optionally substituted by G, especiallynaphthylene, biphenylene, styrylene, anthrylene, or pyrenylene, whichare optionally substituted by C₁-C₁₂alkyl, halogen, —OR²⁰¹, —SR²⁰²and/or —NR²⁰³R²⁰⁴, whereinR²⁰¹ is hydrogen, C₁-C₂₄alkyl, C₁-C₂₄alkyl, which is substituted by Eand/or interrupted by D; C₂-C₁₂alkenyl, C₃-C₆alkenoyl, C₃-C₈cycloalkyl,or benzoyl, each of which may optionally be substituted by one or moregroups C₁-C₆alkyl, halogen, —OH and/or C₁-C₄alkoxy; C₆-C₁₄aryl,especially phenyl, naphthyl, phenanthryl, anthranyl, or pyrenyl, each ofwhich may optionally be substituted by halogen, —OH, C₁-C₁₂alkyl,C₁-C₁₂alkoxy, phenoxy, C₁-C₁₂alkylsulfanyl, phenylsulfanyl,—N(C₁-C₁₂alkyl)₂ and/or diphenylamino;R²⁰² is C₁-C₂₄alkyl, C₁-C₂₄alkyl, which is substituted by E and/orinterrupted by D; C₂-C₁₂alkenyl, C₁-C₈alkanoyl, C₂-C₁₂alkenyl,C₃-C₆alkenoyl; C₃-C₈cycloalkyl, or benzoyl, each of which may optionallybe substituted by one or more groups C₁-C₆alkyl, halogen, —OH,C₁-C₄alkoxy or C₁-C₄alkylsulfanyl; C₆-C₁₄aryl, especially phenyl,naphthyl, phenanthryl, anthranyl, or pyrenyl, each of which mayoptionally be substituted by halogen, C₁-C₁₂alkyl, C₁-C₁₂alkoxy,phenyl-C₁-C₃alkyloxy, phenoxy, C₁-C₁₂alkylsulfanyl, phenylsulfanyl,—N(C₁-C₁₂alkyl)₂, diphenylamino, —(CO)O(C₁-C₈alkyl), —(CO)—C₁-C₈alkyl,or (CO)N(C₁-C₈alkyl)₂;R²⁰³ and R²⁰⁴ are independently of each other hydrogen, C₁-C₂₄alkyl,C₁-C₂₄alkyl, which is substituted by E and/or interrupted by D;C₂-C₅alkenyl, C₃-C₈cycloalkyl, or benzoyl, each of which may optionallybe substituted by one or more groups C₁-C₆alkyl, halogen, —OH, orC₁-C₄alkoxy; phenyl-C₁-C₃alkyl, C₁-C₈alkanoyl, C₃-C₁₂alkenoyl,C₆-C₁₄aryl, especially phenyl naphthyl, phenanthryl anthranyl, orpyrenyl, each of which is optionally substituted by C₁-C₁₂alkyl, benzoylor C₁-C₁₂alkoxy; or R²⁰³ and R²⁰⁴ together are C₂-C₈alkylene, orbranched C₂-C₈alkylene optionally interrupted by —O—, —S—, or —NR²⁰⁵—and/or optionally substituted by hydroxyl, C₁-C₄alkoxy,C₂-C₄alkanoyloxy, or benzoyloxy, wherein the ring formed by R²⁰³ andR²⁰⁴ can optionally be condensed one or two times by phenyl which can besubstituted one to three times with C₁-C₈-alkyl, C₁-C₈-alkoxy, halogen,or cyano;R²⁰⁵ is hydrogen, C₁-C₂₄alkyl, C₁-C₂₄alkyl, which is substituted by Eand/or interrupted by D; C₂-C₅alkenyl, C₃-C₈cycloalkyl,phenyl-C₁-C₃alkyl, C₁-C₈alkanoyl, C₃-C₁₂alkenoyl, C₆-C₁₄aryl, especiallybenzoyl; phenyl, naphthyl, phenanthryl, anthranyl, or pyrenyl, each ofwhich is optionally substituted by C₁-C₁₂alkyl, benzoyl, orC₁-C₁₂alkoxy;D is —CO—, —COO—, —OCOO—, —S—, —SO—, —SO₂—, —O—, —NR⁵—, —SiR⁶¹R⁶²—,—POR⁵—, —CR⁶³═CR⁶⁴—, or —C≡C—;E is halogen, C₆-C₁₄aryl, especially phenyl, naphthyl, phenanthryl,anthranyl, or pyrenyl, which may be substituted by —OR⁵, —SR⁵, —NR⁵R⁶,

SiR⁶²R⁶³R⁶⁴ wherein R⁶², R⁶³ and R⁶⁴ are independently of each other aC₁-C₈alkyl group, a C₆-C₂₄aryl group or a C₇-C₁₂aralkylgroup, —CN,cyclic ether and/or —B(OR⁶⁵)₂, wherein R⁶⁵ is hydrogen, C₁-C₂₄alkyl,C₃-C₈cycloalkyl, C₇-C₂₄aralkyl, C₂-C₁₈alkenyl, C₂-C₂₄alkynyl, hydroxy,mercapto, C₁-C₂₄alkoxy, C₁-C₂₄alkylthio, C₆-C₃₀aryl, C₂-C₃₀heteroaryl,halogen, especially fluorine, haloalkane, silyl, siloxanyl, and analicyclic ring formed with adjacent substituents R⁶⁵; —OR⁵, —SR⁵,—NR⁵R⁶, —COR⁸³—COOR⁷, —CONR⁵R⁶, —CN, halogen, silyl, C₁-C₁₈alkyl, orheteroaryl,G is E, or C₁-C₁₈alkyl, wherein R⁵ and R⁶ are independently of eachother H, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl,C₁-C₁₈alkoxy, or silyl; C₁-C₁₈alkyl or C₁-C₁₈alkyl which is interruptedby —O—; orR⁵ and R⁶ together form a five or six membered ring, in particular

R⁷ is H, C₆-C₁₈aryl, C₇-C₁₂alkylaryl, which are optionally substitutedby C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which isinterrupted by —O—;R⁸ is C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl, C₇-C₁₂alkylaryl, or C₁-C₁₈alkyl which isinterrupted by —O—;R⁶¹ and R⁶² are independently of each other C₆-C₁₈aryl; C₆-C₁₈aryl whichis substituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy; or C₁-C₁₈alkyl which isinterrupted by —O—, andR⁶³ and R⁶⁴ are independently of each other H, C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy; or C₁-C₁₈alkyl whichis interrupted by —O—; with the proviso that at least one of R⁸¹, R⁸²,R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷ and R⁸⁸ is different from H, —OR²⁰¹, —SR²⁰² andC₁-C₂₄alkyl; and the further proviso that the following compounds areexcluded:

Preferably, the compound or compounds of the present invention emitlight below about 520 nm, in particular between about 380 nm and about520 nm.

The compound or compounds of the present invention have especially aNTSC coordinate of between about (0.12, 0.05) and about (0.16, 0.10),very especially a NTSC coordinate of about (0.14, 0.08).

The compound or compounds of the present invention have a melting pointabove about 150° C., preferably above about 200° C. and most preferredabove about 250° C.

To obtain organic layers of this invention with the proper T_(g), orglass transition temperature, it is advantageous that the presentorganic compounds have a glass transition temperature greater than about100° C., for example greater than about 110° C., for example greaterthan about 120° C., for instance greater than about 130° C.

In one embodiment of the present invention compounds of formula I, or IIare preferred, wherein at least one of the groups R⁸¹, R⁸², R⁸³, R⁸⁴,R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸, R⁹¹, R⁹², R⁹³, R⁹⁴, R⁹⁵R⁹⁶, R⁹⁷, R^(91′), R^(92′),R^(93′), R^(94′), R^(95′) R^(96′) and R^(97′) is a C₇-C₃₀aryl group,especially a polycyclic C₈-C₃₀aryl group. Compounds of formula I, or IIare even more preferred, wherein at least two of the groups R⁸¹, R⁸²,R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸, R⁹¹, R⁹², R⁹³, R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷,R^(91′), R^(92′), R^(93′), R^(94′), R^(95′), R^(96′) and R^(97′) are aC₇-C₃₀aryl group, especially a polycyclic C₈-C₃₀aryl group.

In a further embodiment of the present invention compounds of formulaare preferred, wherein M is a single bond,

whereinn1, n2, n3, n4, n5, n6 and n7 are integers of 1 to 10, in particular 1to 3,A⁶ and A⁷ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is substituted by E′ and/or interrupted by D′, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G′, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G′, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E′and/or interrupted by D′, C₇-C₂₅aralkyl, or —CO-A²⁸,A⁸ is C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E′ and/orinterrupted by D′, C₆-C₂₄ aryl, or C₇-C₂₅aralkyl,A⁹ and A¹⁰ are independently of each other C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is substituted by E′ and/or interrupted by D′, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G′, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G′, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E′and/or interrupted by D′, or C₇-C₂₅aralkyl, orA⁹ and A¹⁰ form a ring, especially a five- or six-membered ring, whichcan optionally be substituted by one or more C₁-C₁₈ alkyl groups;A¹⁴ and A¹⁵ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is substituted by E′ and/or interrupted by D′, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G′, C₂-C₂₀heteroaryl, orC₂-C₂₀heteroaryl which is substituted by G′,D′ is —CO—; —COO—; —S—; —SO—; —SO₂—; —O—; —NA²⁵-; —SiA³⁰A³¹-; —POA³²-;—CA²³=CA²⁴-; or —C≡C—; andE′ is —OA²⁹; —SA²⁹; —NA²⁵A²⁶; —COA²⁸; —COOA²⁷; —CONA²⁵A²⁶; —CN;—OCOOA²⁷; or halogen; G′ is E′, or C₁-C₁₈alkyl; wherein A²³, A²⁴, A²⁵and A²⁶ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈aryl whichis substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl, orC₁-C₁₈alkyl which is interrupted by —O—; or A²⁵ and A²⁶ together form afive or six membered ring, in particular

A²⁷ and A²⁸ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl, orC₁-C₁₈alkyl which is interrupted by —O—,A²⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl,or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by—O—,A³⁰ and A³¹ are independently of each other C₁-C₁₈alkyl, C₆-C₁₈aryl, orC₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, andA³² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted byC₁-C₁₈alkyl.

Preferably, A⁶ and A⁷ are independently of each other H, C₁-C₁₈alkyl,such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl,sec-butyl, t-butyl, 2-methylbutyl, n-pentyl, isopentyl, n-hexyl,2-ethylhexyl, or n-heptyl, C₁-C₁₈alkyl which is substituted by E′ and/orinterrupted by D′, such as —CH₂OCH₃, —CH₂OCH₂CH₃, —CH₂OCH₂CH₂OCH₃, or—CH₂OCH₂CH₂OCH₂CH₃, C₆-C₂₄aryl, such as phenyl, naphthyl, or biphenyl,C₆-C₂₄aryl which is substituted by G′, such as —C₆H₄OCH₃, —C₆H₄OCH₂CH₃,—C₆H₃(OCH₃)₂,

or —C₆H₃(OCH₂CH₃)₂, —C₆H₄—CH₃, —C₆H₃(CH₃)₂, —C₆H₂(CH₃)₃, or —C₆H₄tBu.

A⁸ is preferably H, C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl,n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, n-heptyl, or C₆-C₂₄aryl,such as phenyl, naphthyl, or biphenyl.

Preferably, A⁹ and A¹⁰ are independently of each other H, C₁-C₁₈alkyl,such as n-butyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, C₁-C₁₈alkylwhich is substituted by E′ and/or interrupted by D′, such as—CH₂(OCH₂CH₂)_(w)OCH₃, w=1, 2, 3, or 4, C₆-C₂₄aryl, such as phenyl,naphthyl, or biphenyl, C₆-C₂₄aryl which is substituted by G′, such as—C₆H₄OCH₃, —C₆H₄OCH₂CH₃, —C₆H₃(OCH₃)₂, —C₆H₃(OCH₂CH₃)₂, —C₆H₄—CH₃,—C₆H₃(CH₃)₂, —C₆H₂(CH₃)₃, or —C₆H₄tBu, or A⁹ and A¹⁰ together form a 4to 8 membered ring, especially a 5 or 6 membered ring, such ascyclohexyl, or cyclopentyl.

Preferably, A¹⁴ and A¹⁵ are independently of each other H, C₁-C₁₈alkyl,such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, orsec-butyl, or C₆-C₂₄aryl, such as phenyl, naphthyl, or biphenyl.

D′ is preferably —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, —NA²⁵-, wherein A²⁵is C₁-C₁₈alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, or sec-butyl, or C₆-C₂₄aryl, such as phenyl, naphthyl, orbiphenyl.

E′ is preferably —OA²⁹; —SA²⁹; —NA²⁵A²⁵; —COA²⁸; —COOA²⁷; —CONA²⁵A²⁵; or—CN; wherein A²⁵, A²⁷, A²⁸ and A²⁹ are independently of each otherC₁-C₁₈alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl,isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C₆-C₂₄ aryl,such as phenyl, naphthyl, or biphenyl.

Among the above-mentioned groups M the following groups are preferred:

Examples of especially preferred groups M are:

wherein A⁸ and A⁹ are independently of each other C₁-C₁₈alkyl, orcyclohexan;

wherein A⁶ and A⁷ are independently of each other H, or C₁-C₁₈alkyl; or

Groups M having a polycyclic C₈-C₃₀arylen group, or a polycyclicC₄-C₂₆heteroarylen group, wherein polycyclic ring system comprises atleast 8 atoms, are preferred,

and

are most preferred.

Among the compounds of formula II compounds of formula

Compounds of formula

are even more preferred, wherein R⁹⁵ and R^(95′) are independently ofeach other C₁-C₂₄alkyl, or C₆-C₁₄aryl, especially phenyl, naphthyl,phenanthryl, anthranyl, or pyrenyl, which may be substituted by one, ormore C₁-C₈alkyl, or C₁-C₈alkoxy groups, such as a group of formula

R⁴¹, R^(41′), R⁴² and R^(42′) are independently of each other ishydrogen, C₁-C₈alkyl, or C₁-C₈alkoxy, R^(45′) is hydrogen, phenyl, or1-naphthyl, which can be substituted by one, or more C₁-C₈alkyl, orC₁-C₈alkoxy groups; or C₁-C₈alkyl, or C₁-C₈alkoxy.

In another embodiment compounds of formula IIb are preferred, wherein Mis a single bond, R⁹⁶ and R^(96′) are a group

and R⁹¹, R⁹², R⁹³, R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷, R^(91′), R^(92′), R^(93′),R^(94′), R^(95′), R^(96′) and R^(97′) are hydrogen.

Examples of especially preferred compounds are:

In further preferred embodiment of the present invention at least one,preferably two of the groups R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸,R⁹¹, R⁹², R⁹³, R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷, R^(91′), R^(92′), R^(93′), R^(94′),R^(95′), R^(96′) and R^(97′) are a group

wherein A^(14′) and A^(15′) are independently of each other H,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,or C₂-C₂₀heteroaryl which is substituted by G, and A^(16′) is H,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,or C₂-C₂₀heteroaryl which is substituted by G; or a polycyclic arylgroup, especially pentalenyl, indenyl, azulenyl, naphthyl, biphenylenyl,as-indacenyl, s-indacenyl, acenaphthylenyl, fluorenyl, phenanthryl,anthracenyl, fluoranthenyl, acephenanthrylenyl, aceanthrylenyl,triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, picenyl, perylenyl,pentacenyl, pentaphenyl, hexacenyl, or hexaphenyl, which can optionallybe substituted by G, wherein D, E and G are as defined above.

Examples of particularly preferred groups are:

wherein R³⁰⁰ is C₁-C₈alkyl, phenyl, which can be substituted by one, ormore C₁-C₈alkyl, or C₁-C₈alkoxy groups, R¹⁴ is hydrogen, C₁-C₈alkyl,phenyl, or 1-naphthyl, which can be substituted by one, or moreC₁-C₈alkyl, or C₁-C₈alkoxy groups; or C₁-C₈alkoxy, andR¹⁸ and R¹⁹ are independently of each other C₁-C₈alkyl, or cyclohexan.

Compounds of formula Ia, Ib and Ic are preferred, wherein R⁸², R⁸⁷, R⁸³,R⁸⁶, R^(83′) and R^(86′) are independently of each other one of theabove groups. R⁸² and R⁸⁷, R⁸³ and R⁸⁶, R^(83′) and R^(86′) can be thesame or different.

In a further preferred embodiment of the present invention at least one,especially two of the groups R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸,R⁹¹, R⁹², R⁹³, R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷, R^(91′), R^(92′), R^(93′), R^(94′),R^(95′), R^(96′) and R^(97′) are independently of each other a group theformula —(W¹)_(a)—(W²)_(b)—W³(Y¹), wherein

a and b are 0, or 1,W¹ and W² are independently of each other a group of formula

W³ is a group of formula

R¹¹, R^(11′), R¹², R^(12′), R¹³, R^(13′), R¹⁵, R^(15′), R¹⁶, R^(16′),R¹⁷, R^(17′), R⁴¹, R^(41′), R⁴², R^(42′) R⁴⁴, R^(44′), R⁴⁵, R^(45′)R⁴⁶,R^(46′) R⁴⁷ and R^(47′) are independently of each other H, E, silyl,such as tri(C₁-C₈alkyl)silyl, C₆-C₁₈aryl; C₆-C₁₈aryl which issubstituted by G; C₁-C₁₈alkyl; C₁-C₁₈alkyl which is substituted by Eand/or interrupted by D; C₁-C₁₈alkoxy; or C₁-C₁₈alkoxy which issubstituted by E and/or interrupted by D; C₇-C₁₈aralkyl; orC₇-C₁₈aralkyl which is substituted by G;R¹⁴ is H, silyl, such as tri(C₁-C₈alkyl)silyl, C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is substituted by E and/or interrupted by D;C₁-C₁₈alkoxy; or C₁-C₁₈alkoxy which is substituted by E and/orinterrupted by D;

R¹⁸ and R¹⁹ are independently of each other C₁-C₁₈alkyl; C₁-C₁₈alkoxy,C₆-C₁₈aryl; C₇-C₁₈aralkyl; or R¹⁸ and R¹⁹ together form a ringespecially a five- or six-membered ring, which can optionally besubstituted by C₁-C₈alkyl,R²¹, R²², R²³, R²⁴, R²⁵, R²⁶ and R²⁷ are independently of each other H,E, C₁-C₁₈alkyl; C₁-C₁₈alkyl which is substituted by E and/or interruptedby D; C₇-C₁₈aralkyl; C₇-C₁₈aralkyl which is substituted by G; orW³ is a group of formula

R³¹⁵ and R³¹⁶ are independently of each other a hydrogen atom, aC₁-C₁₈alkyl group, a C₁-C₁₈alkoxy group, a group of formula

wherein R³¹⁸, R³¹⁹ and R³²⁰ independently from each other stand forhydrogen, C₁-C₈-alkyl, C₁-C₈-alkoxy, or phenyl, andR³¹⁷ stands for is a hydrogen atom, a C₁-C₂₅alkyl group, which might beinterrupted by —O—, a cycloalkyl group, a C₇-C₁₈aralkyl group, aC₆-C₁₈aryl group, or a heterocyclic group, which may be substituted byG; whereinD is —CO—, —COO—, —OCOO—, —S—, —SO—, —SO₂—, —O—, —NR⁵—, SiR⁶¹R⁶²—,—POR⁵—, —CR⁶³═CR⁶⁴—, or —C≡C—;E is —OR⁵, —SR⁵, —NR⁵R⁶, —COR⁸, —COOR⁷, —OCOOR⁷, —CONR⁵R⁶, —CN, orhalogen;G is E, or C₁-C₁₈alkyl; wherein R⁵ and R⁶ are independently of eachother C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is interrupted by —O—;orR⁵ and R⁶ together form a five or six membered ring, in particular

R⁷ is C₇-C₁₂alkylaryl; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interruptedby —O—;R⁸ is C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl; C₇-C₁₂alkylaryl, or C₁-C₁₈alkyl which isinterrupted by —O—;R⁶¹ and R⁶² are independently of each other C₆-C₁₈aryl; C₆-C₁₈aryl whichis substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₁₈alkyl which isinterrupted by —O—, andR⁶³ and R⁶⁴ are independently of each other H, C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy; or C₁-C₁₈alkyl whichis interrupted by —O—.

If W³ is derived from a heteroaromatic group, it is preferably a groupof formula

wherein R³¹⁷ is C₁-C₁₈alkyl.

Examples of preferred groups W¹ and W² are

wherein R¹¹ is hydrogen, or C₁-C₈alkyl.

Examples of preferred groups W³ are

wherein R¹⁴, R^(41′) and R⁴⁴ are hydrogen, phenyl, tri(C₁-C₈alkyl)silyl,or C₁-C₈alkyl, R¹⁸ and R¹⁹ are independently of each other C₁-C₈alkyl,or cyclohexan.

Examples of preferred groups —(W¹)_(a)—(W²)_(b)—W³ are

wherein R¹¹, R¹⁴, R¹⁸ and R¹⁹ are independently of each other hydrogen,or C₁-C₈alkyl.

Among the compounds of formula I compounds of formula

are more preferred, wherein R⁸², R⁸³, R⁸⁶ and R⁸⁷ are independently ofeach other a group the formula —(W¹)_(a)—(W²)_(b)—W³. R⁸², R⁸³, R⁸⁶ andR⁸⁷ can be different, but are preferably the same; and R⁸¹ and R⁸⁸ areas defined above.

In a preferred embodiment of the present invention at least one,preferably two of the substituents R⁸², R⁸³, R⁸⁶, R⁸⁷, R⁸¹ and R⁸⁸ are

Compounds of formula Ia are even more preferred, wherein R⁸³ and R⁸⁶ are

In a further preferred embodiment of the present invention compounds offormula

are preferred, wherein R⁸¹, R⁸³ and R⁸³ a group the formula —(W²)—W³,whereinW² is a group

wherein R^(13′) and R¹⁷ are independently of each other C₁-C₁₈alkyl, orC₁-C₁₈alkoxy,W³ is a group

A further preferred embodiment of the present invention is directed tocompounds of formula Ia and Ib, wherein at least R⁸² and at least R⁸³are a group of formula

wherein A^(14′) and A¹⁵ are independently of each other H, C₁-C₁₈alkyl,C₆-C₂₄aryl, or phenyl, which is substituted by one, or more C₁-C₈alkyl,or C₁-C₈alkoxy groups and the other, and R⁸⁷ and R⁸⁶ are a group offormula

or a group of formula —(W¹)_(a)—(W²)_(b)—W³.

A further preferred embodiment of the present invention is directed tocompounds of formula

(Ic), wherein R^(83′) and R^(86′) are independently of each other H,C₁-C₁₈alkyl,

wherein R¹⁴ is hydrogen, phenyl, tri(C₁-C₈alkyl)silyl, or C₁-C₈alkyl,R¹⁸ and R¹⁹ are independently of each other C₁-C₈alkyl, or cyclohexan.

Examples of especially preferred compounds are given below:

Particularly suitable dibenzo-, dinaphthofurans are compounds A-1, A-2,A-4, A-5, A-10, A-11, A-16, A-19, B-1 and B-2.

In another preferred embodiment at least one, preferably two of thesubstituents R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸, R⁹¹, R⁹², R⁹³, R⁹⁴,R⁹⁵, R⁹⁶, R⁹⁷, R^(91′), R^(92′), R^(93′), R^(94′), R^(95′), R^(96′) andR^(97′) are independently of each other a group of the formula—W₁—(W²)_(b)—W³ (Y²), wherein b is 0, or, 1, W¹ and W² are as definedabove and are preferably independently of each other a group of formula

especiallyW³ is a group of formula —NR⁷⁰R⁷¹, wherein R⁷⁰ and R⁷¹ are independentlyof each other a group of formula

wherein R⁷², R⁷³ and R⁷⁴ are independently of each other hydrogen,C₁-C₈alkyl, a hydroxyl group, a mercapto group, C₁-C₈alkoxy,C₁-C₈alkylthio, halogen, halo-C₁-C₈alkyl, a cyano group, an aldehydegroup, a ketone group, a carboxyl group, an ester group, a carbamoylgroup, an amino group, a nitro group, a silyl group or a siloxanylgroup, or R⁷⁰ and R⁷¹ together with the nitrogen atom to which they arebonded form a five or six membered heterocyclic ring, such as

which can be condensed by one or two optionally substituted phenylgroups, such as

wherein R²¹⁶ and R²¹⁷ independently from each other stands for hydrogen,C₁-C₈alkyl, C₁-C₈alkoxy, or phenyl, andX¹ stands for hydrogen, or C₁-C₈alkyl;R⁷⁵, R⁷⁶, R⁷⁷ and R⁷⁸ are independently of each other H, E, C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by E; C₁-C₁₈alkyl; C₁-C₁₈alkyl which issubstituted by G and/or interrupted by D; C₇-C₁₈aralkyl; orC₇-C₁₈aralkyl which is substituted by E; wherein D, E, G, R¹¹, R^(11′),R^(12′), R¹⁶R^(16′), R¹⁷, R^(17′), R¹⁸, R¹⁹, R³⁰, R³¹, R³² and R³³ areas defined above, and R^(30′), R^(31′), R^(82′) and R^(33′)independently of each other have the meaning of R³⁰.

If R⁷⁰ and R⁷¹ are independently of each other a group of formula

b is preferably 1.

In said embodiment groups of the formula —W¹—(W²)_(b)—W³ are morepreferred, wherein b is 0, or 1, W¹ and W² are independently of eachother a group of formula

W³ is a group of formula

or —NR⁷⁰R⁷¹, wherein R⁷⁰ and R⁷¹ are independently of each other a groupof formula

wherein R⁷² is C₁₋₁₈alkyl.

In said embodiment of the present invention compounds of formula Ia andIb are preferred, wherein R⁸² and R⁸⁷ and R⁸³ and R⁸⁶ are independentlyof each other a group of formula —(W²)_(b)—W³. The groups —(W²)_(b)—W³can be different, but are preferably the same.

Examples of preferred compounds are given below:

In another preferred embodiment the present invention is directed tocompounds of formula I wherein at least one of R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵,R⁸⁶, R⁸⁷ and R⁸⁸ is a group Y¹ and at least one of R⁸¹, R⁸², R⁸³, R⁸⁴,R⁸⁵, R⁸⁶, R⁸⁷ and R⁸⁸ is a group Y².

In said embodiment compounds of formula Ia are preferred, wherein R⁸¹ isH, R⁸⁸ is Y² and R⁸³ and R⁸⁶ are Y¹; or R⁸¹ and R⁸⁸ are H, R⁸³ is Y² andR⁸⁶ are Y¹.

Examples of preferred compounds are given below:

The present benzofuran compounds show a high solid state fluorescence inthe desired wavelength range and can be prepared according to oranalogous to known procedures (see, for example, WO99/47474,WO2004039786 and WO2004077885).

The benzofuran compounds of the present invention of the formula:

wherein W³ is as defined above,can, for example, be prepared according to a process, which comprisesreacting a derivative of formula

wherein R¹⁰⁰ stands for halogen such as chloro or bromo, preferablybromo, or E having the meaning of

wherein a is 2 or 3,with boronic acid derivativeE-W³, or—in case R¹⁰⁰ is not halogen—Hal-W³,wherein Hal stands for halogen, preferably for bromo, in the presence ofan allylpalladium catalyst of theμ-halo(triisopropylphosphine)(η³-allyl)palladium(II) type (see forexample WO99/47474).

Preferably, the reaction is carried out in the presence of an organicsolvent, such as an aromatic hydrocarbon or a usual polar organicsolvent, such as benzene, toluene, xylene, tetrahydrofurane, or dioxane,or mixtures thereof, most preferred toluene. Usually, the amount of thesolvent is chosen in the range of from 1 to 10 l per mol of boronic acidderivative. Also preferred, the reaction is carried out under an inertatmosphere such as nitrogen, or argon.

Further, it is preferred to carry out the reaction in the presence of anaqueous base, such as an alkali metal hydroxide or carbonate such asNaOH, KOH, Na₂CO₃, K₂CO₃, Cs₂CO₃ and the like, preferably an aqueousK₂CO₃ solution is chosen. Usually, the molar ratio of the base tocompound III is chosen in the range of from 0.5:1 to 50:1.

Generally, the reaction temperature is chosen in the range of from 40 to180° C., preferably under reflux conditions.

Preferred, the reaction time is chosen in the range of from 1 to 80hours, more preferably from 20 to 72 hours.

In a preferred embodiment a usual catalyst for coupling reactions or forpolycondensation reactions is used, preferably Pd-based catalyst such asknown tetrakis(triarylphosphonium)-palladium, preferably (Ph₃P)₄Pd andderivatives thereof. Usually, the catalyst is added in a molar ratiofrom inventive DPP polymer to the catalyst in the range of from 100:1 to10:1, preferably from 50:1 to 30:1.

Also preferred, the catalyst is added as in solution or suspension.Preferably, an appropriate organic solvent such as the ones describedabove, preferably benzene, toluene, xylene, THF, dioxane, morepreferably toluene, or mixtures thereof, is used. The amount of solventusually is chosen in the range of from 1 to 10 l per mol of boronic acidderivative.

The obtained inventive polymer can be isolated by well-known methods.Preferably, after cooling down the reaction mixture to room temperature,it is poured into acetone and the obtained precipitation is filteredoff, washed and dried.

C₁-C₁₈Alkyl is a branched or unbranched radical such as for examplemethyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl,tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, or octadecyl.

C₁-C₁₈Alkoxy radicals are straight-chain or branched alkoxy radicals,e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy,isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy,pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy.

C₂-C₁₈Alkenyl radicals are straight-chain or branched alkenyl radicals,such as e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl,isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl,n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.

C₂₋₂₄Alkynyl is straight-chain or branched and preferably C₂₋₈alkynyl,which may be unsubstituted or substituted, such as, for example,ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl,2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl,1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl,trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl,1-nonyn-9-yl, 1-decyn-10-yl or 1-tetracosyn-24-yl.

C₄-C₁₈cycloalkyl is preferably C₅-C₁₂cycloalkyl, such as, for example,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,cyclodecyl, cyclododecyl. Cyclohexyl and cyclododecyl are mostpreferred.

The term “aryl group” is typically C₆-C₃₀aryl, such as phenyl, indenyl,azulenyl, naphthyl, biphenyl, terphenylyl or quadphenylyl, as-indacenyl,s-indacenyl, acenaphthylenyl, phenanthryl, fluoranthenyl, triphenlenyl,chrysenyl, naphthacen, picenyl, perylenyl, pentaphenyl, hexacenyl,pyrenyl, or anthracenyl, preferably phenyl, 1-naphthyl, 2-naphthyl,9-phenanthryl, 2- or 9-fluorenyl, 3- or 4-biphenyl, which may beunsubstituted or substituted. Examples of C₆-C₁₈aryl are phenyl,1-naphthyl, 2-naphthyl, 3- or 4-biphenyl, 9-phenanthryl, 2- or9-fluorenyl, which may be unsubstituted or substituted.

C₇-C₂₄aralkyl radicals are preferably C₇-C₁₈aralkyl radicals, which maybe substituted, such as, for example, benzyl, 2-benzyl-2-propyl,β-phenyl-ethyl, α,α-dimethyl benzyl, ω-phenyl-butyl,ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl, ω-phenyl-octadecyl,ω-phenyl-eicosyl or ω-phenyl-docosyl, preferably C₇-C₁₈aralkyl such asbenzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl,ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl orω-phenyl-octadecyl, and particularly preferred C₇-C₁₂aralkyl such asbenzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl,ω-phenyl-butyl, or ω,ω-dimethyl-ω-phenyl-butyl, in which both thealiphatic hydrocarbon group and aromatic hydrocarbon group may beunsubstituted or substituted.

C₇-C₁₂alkylaryl is, for example, a phenyl group substituted with one,two or three C₁-C₆alkyl groups, such as, for example, 2-, 3-, or4-methylphenyl, 2-, 3-, or 4-ethylphenyl, 3-, or 4-isopropylphenyl,3,4-dimethylphenyl, 3,5-dimethylphenyl, or 3,4,5-trimethylphenyl.

The term “heteroaryl group”, especially C₂-C₃₀heteroaryl, is a ring,wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and istypically an unsaturated heterocyclic radical with five to 18 atomshaving at least six conjugated π-electrons such as thienyl,benzo[b]thienyl, dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl,2H-pyranyl, benzofuranyl, isobenzofuranyl, 2H-chromenyl, xanthenyl,dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl,pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, 1H-pyrrolizinyl,isoindolyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, 3H-indolyl,phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl,indazolyl, purinyl, quinolizinyl, chinolyl, isochinolyl, phthalazinyl,naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl,carbazolyl, 4aH-carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl,phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl,isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl,preferably the above-mentioned mono- or bicyclic heterocyclic radicals,which may be unsubstituted or substituted.

Halogen is fluorine, chlorine, bromine and iodine.

The terms “haloalkyl” mean groups given by partially or whollysubstituting the above-mentioned alkyl group, with halogen, such astrifluoromethyl etc. The “aldehyde group, ketone group, ester group,carbamoyl group and amino group” include those substituted by an alkylgroup, a cycloalkyl group, an aryl group, an aralkyl group or aheterocyclic group, wherein the alkyl group, the cycloalkyl group, thearyl group, the aralkyl group and the heterocyclic group may beunsubstituted or substituted. The term “silyl group” means a group offormula —SiR⁶²R⁶³R⁶⁴, wherein R⁶², R⁶³ and R⁶⁴ are independently of eachother a C₁-C₈alkyl group, in particular a C₁-C₄alkyl group, a C₆-C₂₄arylgroup or a C₇-C₁₂aralkylgroup, such as a trimethylsilyl group. The term“siloxanyl group” means a group of formula —O—SiR⁶²R⁶³R⁶⁴, wherein R⁶²,R⁶³ and R⁶⁴ are as defined above, such as a trimethylsiloxanyl group.

Possible substituents of the above-mentioned groups are C₁-C₈alkyl, ahydroxyl group, a mercapto group, C₁-C₈alkoxy, C₁-C₈alkylthio, halogen,halo-C₁-C₈alkyl, a cyano group, an aldehyde group, a ketone group, acarboxyl group, an ester group, a carbamoyl group, an amino group, anitro group or a silyl group.

As described above, the aforementioned radicals may be substituted by Eand/or, if desired, interrupted by D. Interruptions are of coursepossible only in the case of radicals containing at least 2 carbon atomsconnected to one another by single bonds; C₆-C₁₈aryl is not interrupted;interrupted arylalkyl or alkylaryl contains the unit D in the alkylmoiety. C₁-C₁₈alkyl substituted by one or more E and/or interrupted byone or more units D is, for example, (CH₂CH₂O)_(n)—R^(x), where n′ is anumber from the range 1-9 and R^(x) is H or C₁-C₁₀alkyl orC₂-C₁₀alkanoyl (e.g. CO—CH(C₂H₅)C₄H₉), CH₂—CH(OR^(y)′)—CH₂—O—R^(y),where R^(y) is C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, phenyl,C₇-C₁₅-phenylalkyl, and R^(y)′ embraces the same definitions as R^(y) oris H; C₁-C₈alkylene-COO—R^(z), e.g. CH₂COOR^(z), CH(CH₃)COOR^(z),C(CH₃)₂COOR^(z), where R^(z) is H, C₁-C₁₈alkyl, (CH₂CH₂O)₁₋₉—R^(x), andR^(x) embraces the definitions indicated above; CH₂CH₂—O—CO—CH═CH₂;CH₂CH(OH)CH₂—O—CO—C(CH₃)═CH₂.

The electroluminescent devices may be employed for full color displaypanels in, for example, mobile phones, televisions and personal computerscreens.

The electroluminescent devices of the present invention are otherwisedesigned as is known in the art, for example as described in U.S. Pat.Nos. 5,518,824, 6,225,467, 6,280,859, 5,629,389, 5,486,406, 5,104,740,5,116,708 and 6,057,048, the relevant disclosures of which are herebyincorporated by reference.

For example, organic EL devices contain one or more layers such as:

substrate; base electrode; hole-injecting layer; hole transportinglayer; emitter layer; electron-transporting layer; electron-injectinglayer; top electrode; contacts and encapsulation.

This structure is a general case and may have additional layers or maybe simplified by omitting layers so that one layer performs a pluralityof tasks. For instance, the simplest organic EL device consists of twoelectrodes which sandwich an organic layer that performs all functions,including the function of light emission.

A preferred EL device comprises in this order:

(a) an anode,(b) a hole injecting layer and/or a hole transporting layer,(c) a light-emitting layer,(d) optionally an electron transporting layer and(e) a cathode.

The benzofuran compounds of the present invention can, in principal beused for any organic layer, such as, for example, hole transportinglayer, light emitting layer, or electron transporting layer, but arepreferably used as the light emitting material in the light emittinglayer, optionally as a host or guest component, or electron transportinglayer.

In particular, the present organic compounds function as light emittersand are contained in the light emission layer or form the light-emittinglayer.

The light emitting compounds of this invention exhibit intensefluorescence in the solid state and have excellentelectric-field-applied light emission characteristics. Further, thelight emitting compounds of this invention are excellent in theinjection of holes from a metal electrode and the transportation ofholes; as well as being excellent in the injection of electrons from ametal electrode and the transportation of electrons. They areeffectively used as light emitting materials and may be used incombination with other hole transporting materials, other electrontransporting materials or other dopants.

The organic compounds of the present invention form uniform thin films.The light emitting layers may therefore be formed of the present organiccompounds alone.

Alternatively, the light-emitting layer may contain a knownlight-emitting material, a known dopant, a known hole transportingmaterial or a known electron transporting material as required. In theorganic EL device, a decrease in the brightness and life caused byquenching can be prevented by forming it as a multi-layered structure.The light-emitting material, a dopant, a hole-injecting material and anelectron-injecting material may be used in combination as required.Further, a dopant can improve the light emission brightness and thelight emission efficiency, and can attain the red or blue lightemission. Further, each of the hole transporting zone, thelight-emitting layer and the electron transporting zone may have thelayer structure of at least two layers. In the hole transporting zone inthis case, a layer to which holes are injected from an electrode iscalled “hole-injecting layer”, and a layer which receives holes from thehole-injecting layer and transport the holes to a light-emitting layeris called “hole transporting layer”. In the electron transporting zone,a layer to which electrons are injected from an electrode is called“electron-injecting layer”, and a layer which receives electrons fromthe electron-injecting layer and transports the electrons to alight-emitting layer is called “electron transporting layer”. Theselayers are selected and used depending upon factors such as the energylevel and heat resistance of materials and adhesion to an organic layeror metal electrode.

The light-emitting material or the dopant which may be used in thelight-emitting layer together with the organic compounds of the presentinvention includes for example anthracene, naphthalene, phenanthrene,pyrene, tetracene, coronene, chrysene, fluorescein, perylene,phthaloperylene, naphthaloperylene, perinone, phthaloperinone,naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarine,oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine,cyclopentadiene, quinoline metal complex, aminoquinoline metal complex,benzoquinoline metal complex, imine, diphenylethylene, vinyl anthracene,diaminocarbazole, pyran, thiopyran, polymethine, merocyanine, animidazole-chelated oxynoid compound, quinacridone, rubrene, andfluorescent dyestuffs for a dyestuff laser or for brightening.

It is also possible to use the compounds of the present invention withphosphorescent materials as a dopant in the light-emitting layer.Examples of the phosphorescent materials are, for example, metalcomplexes of Ir, Pt, Eu, Ru, Rh, Pd, Ag, Re, Os and Au and aredescribed, for example, in JP2005-11804 and WO2004/034751.

Examples of typical structures of the metal complex are shown below:

In that case the electroluminescent device may comprise in this order

(a) an anode, such as, for example, ITO,(b1) a hole injecting layer, such as, for example, CuPc,(b2) a hole transporting layer, such as, for example, such as, forexample, N,N′-Di(naphthalene-1-yl)-N,N′-diphenyl-benzidine (NPD), orTCTA,(c) a light-emitting layer, comprising a phosphorescent compound and adibenzofuran compound of the present invention, especially a compoundA-1 to A-66, B-1 to B-18, C-1 and C-2.a positive hole inhibiting layer, such as, for example, BCP, or BAlq,(d) an electron transporting layer, such as, for example, Alq₃, andan inorganic compound layer, such as, for example, LiF,(e) a cathode, such as, for example, Al.

If the dibenzofuran compounds of the present invention are used as hosttogether with guest compounds, such, as for example,2,5,8,11-tetra-t-butylperylene (Jiaumin Shi Ching W. Tang, Appl. Phys.Lett. 80, 3201 (2002), or the compounds, described, for example, inWO03/105538, such as, for example,

the electroluminescent device may comprise in this order(a) an anode, such as, for example, ITO,(b1) a hole injecting layer, such as, for example, CuPc,(b2) a hole transporting layer, such as, for example, NPD, or TCTA,(c) a light-emitting layer, comprising a fluorescent guest compound anda dibenzofuran host compound of the present invention, especially acompound A-1 to A-66, B-1 to B-18, C-1 and C-2,optionally a positive hole inhibiting layer, such as, for example, BCP,(d) an electron transporting layer, such as, for example, Alq₃, or TPBlandan inorganic compound layer, such as, for example, LiF,(e) a cathode, such as, for example, Al.

The weight ratio of compound of the formula I to the dopant in general50:50 to 99.99:0.01, preferably 90:10 to 99.99:0.01, more preferably95:5 to 99.9:0.1. If the guest is a phosphorescent compound, itsconcentration is normally 5-10%.

Accordingly, the present invention also relates to compositionscomprising a compound of the present invention.

The compounds of the present invention and the above compound orcompounds that can be used in a light-emitting layer may be used in anymixing ratio for forming a light-emitting layer. That is, the organiccompounds of the present invention may provide a main component forforming a light-emitting layer, or they may be a doping material inanother main material, depending upon a combination of the abovecompounds with the organic compounds of the present invention.

The hole-injecting material is selected from compounds which are capableof transporting holes, are capable of receiving holes from the anode,have an excellent effect of injecting holes to a light-emitting layer ora light-emitting material, prevent the movement of excitons generated ina light-emitting layer to an electron-injecting zone or anelectron-injecting material and have the excellent capability of forminga thin film. Suitable hole-injecting materials include for example aphthalocyanine derivative, a naphthalocyanine derivative, a porphyrinderivative, oxazole, oxadiazole, triazole, imidazole, imidazolone,imidazolthione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole,oxadiazole, hydrazone, acylhydrazone, polyarylalkane, stilbene,butadiene, benzidine type triphenylamine, styrylamine typetriphenylamine, diamine type triphenylamine, derivatives of these, andpolymer materials such as polyvinylcarbazole, polysilane and anelectroconducting polymer.

In the organic EL device of the present invention, the hole-injectingmaterial which is more effective is an aromatic tertiary aminederivative or a phthalocyanine derivative. Although not speciallylimited, specific examples of the tertiary amine derivative includetriphenylamine, tritolylamine, tolyidiphenylamine,N,N′-diphenyl-N,N′-(3-methylphenyl)-1,1-biphenyl-4,4′-diamine,N,N,N′,N′-tetra(4-methylphenyl)-1,1′-phenyl-4,4′-diamine,N,N,N′,N′-tetra(4-methylphenyl)-1,1′-biphenyl-4,4′-diamine,N,N′-diphenyl-N,N′-di(1-naphthyl)-1,1′-biphenyl-4,4′-diamine,N,N′-di(methylphenyl)-N,N′-di(4-n-butylphenyl)-phenanthrene-9,10-diamine,4,4′,4″-tris(3-methylphenyl)-N-phenylamino)triphenylamine,1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, and oligomers or polymershaving aromatic tertiary amine structures of these.

Although not specially limited, specific examples of the phthalocyanine(Pc) derivative include phthalocyanine derivatives or naphthalocyaninederivatives such as H₂Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc,ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl₂SiPc, (HO)AlPc, (HO)GaPc, VOPc,TiOPc, MoOPc, and GaPc-O—GaPc.

The hole transporting layer can reduce the driving voltage of the deviceand improve the confinement of the injected charge recombination withinthe light emitting layer, comprising the compounds of the presentinvention. Any conventional suitable aromatic amine hole transportingmaterial described for the hole-injecting layer may be selected forforming this layer.

A preferred class of hole transporting materials is comprised of4,4′-bis(9-carbazolyl)-1,1′-biphenyl compounds of the formula

wherein R⁶¹ and R⁶² is a hydrogen atom or an C₁-C₃alkyl group; R⁶³through R⁶⁶ are substituents independently selected from the groupconsisting of hydrogen, a C₁-C₆alkyl group, a C₁-C₆alkoxy group, ahalogen atom, a dialkylamino group, a C₆-C₃₀aryl group, and the like.Illustrative examples of 4,4′-bis(9-carbazolyl)-1,1′-biphenyl compoundsinclude 4,4′-bis(9-carbazolyl)-1,1′-biphenyl and4,4′-bis(3-methyl-9-carbazolyl)-1,1′-biphenyl, and the like; or4,4′,4″-tri-(N-carbazoyl)triphenylamine (TCTA).

In addition, polymeric material can be used as a hole injection materialand a hole transporting material, such as poly(N-vinylcarbazole) (PVK),polythiophenes, polypyrrole, polyaniline, and copolymers such aspoly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate), also calledPEDOT/PSS.

The electron transporting layer is not necessarily required for thepresent device, but is optionally and preferably used for the primarypurpose of improving the electron injection characteristics of the ELdevices and the emission uniformity. Illustrative examples of electrontransporting compounds, which can be utilized in this layer, include themetal chelates of 8-hydroxyquinoline as disclosed in U.S. Pat. Nos.4,539,507, 5,151,629, and 5,150,006, the disclosures of which aretotally incorporated herein by reference.

Examples of suitable electron transporting materials are metal complexcompounds and nitrogen-containing five-membered ring derivatives.

Although not specially limited, specific examples of the metal complexcompound include lithium 8-hydroxyquinolinate, zincbis(8-hydroxyquinolinate), copper bis(8-hydroxyquinolinate), manganesebis(8-hydroxyquinolinate), aluminum tris(8-hydroxyquinolinate), aluminumtris(2-methyl-8-hydroxyquinolinate), gallium tris(8-hydroxyquinolinate),beryllium bis(10-hydroxybenzo[h]quinolinate), zincbis(10-hydroxybenzo[h]quinolinate), chlorogalliumbis(2-methyl-8-quinolinate), galliumbis(2-methyl-8-quinolinate)(o-cresolate), aluminumbis(2-methyl-8-quinolinate)(1-naphtholate), galliumbis(2-methyl-8-quinolinate)(2-naphtholate), galliumbis(2-methyl-8-quinolinate)phenolate, zincbis(o-(2-benzooxazolyl)phenolate), zincbis(o-(2-benzothiazolyl)phenolate) and zincbis(o-(2-benzotrizolyl)phenolate). The nitrogen-containing five-memberedderivative is preferably an oxazole, thiazole, thiadiazole, or triazolederivative. Although not specially limited, specific examples of theabove nitrogen-containing five-membered derivative include2,5-bis(1-phenyl)-1,3,4-oxazole,1,4-bis(2-(4-methyl-5-phenyloxazolyl)benzene,2,5-bis(1-phenyl)-1,3,4-thiazole, 2,5-bis(1-phenyl)-1,3,4-oxadiazole,2-(4′-tert-butylphenyl)-5-(4″-biphenyl)1,3,4-oxadiazole,2,5-bis(1-naphthyl)-1,3,4-oxadiazole,1,4-bis[2-(5-phenyloxadiazolyl)]benzene,1,4-bis[2-(5-phenyloxadiazolyl)-4-tert-butylbenzene],2-(4′-tert-butylphenyl)-5-(4″-biphenyl)-1,3,4-thiadiazole,2,5-bis(1-naphthyl)-1,3,4-thiadiazole,1,4-bis[2-(5-phenylthiazolyl)]benzene,2-(4′-tert-butylphenyl)-5-(4″-biphenyl)-1,3,4-triazole,2,5-bis(1-naphthyl)-1,3,4-triazole and1,4-bis[2-(5-phenyltriazolyl)]benzene. Another class of electrontransport materials are oxadiazole metal chelates, such asbis[2-(2-hydroxyphenyl)-5-phenyl-1,3,4-oxadiazolato]zinc;bis[2-(2-hydroxyphenyl)-5-phenyl-1,3,4-oxadiazolato]beryllium;bis[2-(2-hydroxyphenyl)-5-(1-naphthyl)-1,3,4-oxadiazolato]zinc;bis[2-(2-hydroxyphenyl)-5-(1-naphthyl)-1,3,4-oxadiazolato]beryllium;bis[5-biphenyl-2-(2-hydroxyphenyl)-1,3,4-oxadiazolato]zinc;bis[5-biphenyl-2-(2-hydroxyphenyl)-1,3,4-oxadiazolato]beryllium;bis(2-hydroxyphenyl)-5-phenyl-1,3,4-oxadiazolato]lithium;bis[2-(2-hydroxyphenyl)-5-p-tolyl-1,3,4-oxadiazolato]zinc; bis2-(2-hydroxyphenyl)-5-p-tolyl-1,3,4-oxadiazolato]beryllium;bis[5-(p-tert-butylphenyl)-2-(2-hydroxyphenyl)-1,3,4-oxadiazolato]zinc;bis[5-(p-tert-butylphenyl)-2-(2-hydroxyphenyl)-1,3,4-oxadiazolato]beryllium;bis[2-(2-hydroxyphenyl)-5-(3-fluorophenyl)-1,3,4-oxadiazolato]zinc;bis[2-(2-hydroxyphenyl)-5-(4-fluorophenyl)-1,3,4-oxadiazolato]zinc;bis[2-(2-hydroxyphenyl)-5-(4-fluorophenyl)-1,3,4-oxadiazolato]beryllium;bis[5-(4-chlorophenyl)-2-(2-hydroxyphenyl)-1,3,4-oxadiazolato]zinc;bis[2-(2-hydroxy phenyl)-5-(4-methoxyphenyl)-1,3,4-oxadiazolato]zinc;bis[2-(2-hydroxy-4-methylphenyl)-5-phenyl-1,3,4-oxadiazolato]zinc;bis[2-.alpha.-(2-hydroxynaphthyl)-5-phenyl-1,3,4-oxadiazolato]zinc;bis[2-(2-hydroxyphenyl)-5-p-pyridyl-1,3,4-oxadiazolato]zinc;bis[2-(2-hydroxyphenyl)-5-p-pyridyl-1,3,4-oxadiazolato]beryllium;bis[2-(2-hydroxyphenyl)-5-(2-thiophenyl)-1,3,4-oxadiazolato]zinc;bis[2-(2-hydroxyphenyl)-5-phenyl-1,3,4-thiadiazolato]zinc;bis[2-(2-hydroxyphenyl)-5-phenyl-1,3,4-thiadiazolato]beryllium;bis[2-(2-hydroxyphenyl)-5-(1-naphthyl)-1,3,4-thiadiazolato]zinc; andbis[2-(2-hydroxyphenyl)-5-(1-naphthyl)-1,3,4-thiadiazolato]beryllium,and the like.

Other suitable compounds for the electron transporting material arehetero-cyclic compounds such as benzimidazole derivatives, benzoxazolederivatives, oxadiazole derivatives, thiadiazole derivative, triazolederivatives, pyrazine derivatives, phenanthroline derivatives,quinoxaline derivatives, quinoline derivatives, benzoquinolinederivatives, oligo-pyridine derivatives, e.g. bipyridine derivatives andterpyridine derivatives, naphthylidine derivatives, indole derivativesand naphthalimide derivatives; silole derivatives; and phosphineoxidederivatives.

The property of charge injection can be improved by adding anelectron-accepting compound to the hole injection layer and/or the holetransporting layer and electron-donating material to the electrontransporting layer.

It is possible to add reducing dopant to the electron transporting layerto improve the EL device property. The reducing dopant is a materialthat can reduce the electron transporting material. Examples of thereducing dopant are alkaline metals, e.g. Na, K, Rb and Cs, and alkalineearth metals, e.g. Ca, Sr, and Ba. The organic EL device of the presentinvention may comprise an inorganic compound layer between at least oneof the electrodes and the above organic thin layer. Examples of theinorganic compound used for the inorganic compound layer include varioustypes of oxides, nitrides and oxide nitrides such as alkali metaloxides, alkaline earth metal oxides, rare earth oxides, alkali metalhalides, alkaline earth metal halides, rare earth halides, SiO_(x),AlO_(x), SiN_(x), SiON, AlON, GeO_(x), LiO_(x), LiON, TiO_(x), TiON,TaO_(x), TaON, TaN_(x) and C. In particular, as the component contactingthe anode, SiO_(x), AlO_(x), SiN_(x), SiON, AlON, GeO_(x) and C arepreferred since a suitable interface layer of injection is formed. Asthe component contacting the cathode LiF, MgF₂, CaF₂ and NaF arepreferred.

In the organic EL device of the present invention, the light-emittinglayer may contain, in addition to the light-emitting organic material ofthe present invention, at least one of other light-emitting material,other dopant, other hole-injecting material and other electron-injectingmaterial. For improving the organic EL device of the present inventionin the stability against temperature, humidity and ambient atmosphere, aprotective layer may be formed on the surface of the device, or thedevice as a whole may be sealed with a silicone oil, or the like.

The electrically conductive material used for the anode of the organicEL device is suitably selected from those materials having a workfunction of greater than 4 eV. The electrically conductive materialincludes carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten,silver, gold, platinum, palladium, alloys of these, metal oxides such astin oxide and indium oxide used for ITO substrates or NESA substrates,and organic electroconducting polymers, such as polythiophene andpolypyrrole.

The electrically conductive material used for the cathode is suitablyselected from those having a work function of smaller than 4 eV. Theelectrically conductive material includes magnesium, calcium, tin, lead,titanium, yttrium, lithium, ruthenium, manganese, aluminum and alloys ofthese, while the electrically conductive material shall not be limitedto these. Examples of the alloys include magnesium/silver,magnesium/indium and lithium/aluminum, while the alloys shall not belimited to these. Each of the anode and the cathode may have a layerstructure formed of two layers or more as required.

For the effective light emission of the organic EL device, at least oneof the electrodes is desirably sufficiently transparent in the lightemission wavelength region of the device. Further, the substrate isdesirably transparent as well. The transparent electrode is producedfrom the above electrically conductive material by a deposition methodor a sputtering method such that a predetermined light transmittance issecured. The electrode on the light emission surface side has forinstance a light transmittance of at least 10%. The substrate is notspecially limited so long as it has adequate mechanical and thermalstrength and has transparency. For example, it is selected from glasssubstrates and substrates of transparent resins such as a polyethylenesubstrate, a polyethylene terephthalate substrate, a polyether sulfonesubstrate and a polypropylene substrate.

In the organic EL device of the present invention, each layer can beformed by any one of dry film forming methods such as a vacuumdeposition method, a sputtering method, a plasma method and an ionplating method and wet film forming methods such as a spin coatingmethod, a dipping method and a flow coating method. The thickness ofeach layer is not specially limited, while each layer is required tohave a proper thickness. When the layer thickness is too large,inefficiently, a high voltage is required to achieve predeterminedemission of light. When the layer thickness is too small, the layer isliable to have a pinhole, etc., so that sufficient light emissionbrightness is hard to obtain when an electric field is applied. Thethickness of each layer is for example in the range of from about 5 nmto about 10 μm, for instance about 10 nm to about 0.2 μm.

In the wet film forming method, a material for forming an intended layeris dissolved or dispersed in a proper solvent, such as toluene, ethanol,chloroform, tetrahydrofuran and dioxane, and a thin film is formed fromthe solution or dispersion. The solvent shall not be limited to theabove solvents. For improving the film formability and preventing theoccurrence of pinholes in any layer, the above solution or dispersionfor forming the layer may contain a proper resin and a proper additive.The resin that can be used includes insulating resins such aspolystyrene, polycarbonate, polyarylate, polyester, polyamide,polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylateand cellulose, copolymers of these, photoconductive resins such aspoly-N-vinylcarbozole and polysilane, and electroconducting polymerssuch as polythiophene and polypyrrole. The above additive includes anantioxidant, an ultraviolet absorbent and a plasticizer.

When the light-emitting organic material of the present invention isused in a light-emitting layer of an organic EL device, an organic ELdevice can be improved in organic EL device characteristics such aslight emission efficiency and maximum light emission brightness.Further, the organic EL device of the present invention is remarkablystable against heat and electric current and gives a usable lightemission brightness at a low actuation voltage. The problematicdeterioration of conventional devices can be remarkably decreased.

The organic EL device of the present invention has significantindustrial values since it can be adapted for a flat panel display of anon-wall television set, a flat light-emitting device, a light source fora copying machine or a printer, a light source for a liquid crystaldisplay or counter, a display signboard, lighting application and asignal light.

The material of the present invention can be used in the fields of anorganic EL device, an electrophotographic photoreceptor, a photoelectricconverter, a solar cell, and an image sensor.

Various features and aspects of the present invention are illustratedfurther in the examples that follow. While these examples are presentedto show one skilled in the art how to operate within the scope of thisinvention, they are not to serve as a limitation on the scope of theinvention where such scope is only defined in the claims. Unlessotherwise indicated in the following examples and elsewhere in thespecification and claims, all parts and percentages are by weight.

EXAMPLES Example 1 Synthesis of 2,8-Bis-((E)-styryl)-dibenzofuran

1a) 2,8-Dibromodibenzofuran

Bromine (92.6 g, 0.58 mol) in acetic acid (54 g) is added at 75° C. to asolution of dibenzofuran (23.2 g, 0.14 mol) in acetic acid (232 g). Themixture is then stirred at 75° C. for 3 hours. The reaction mixture iscooled to room temperature and poured into H₂O. The orange solid iswashed with Na₂S₂O₃ aq. and H₂O. The crude product is then purified byrecrystallization from n-hexane, wherein the pure product is obtained asa white solid (38% yield; mp.: 226° C.).

¹H-NMR (CDCl₃, ppm): 7.65 (d, 2H), 7.59 (dd, 2H), 8.03 (d, 2H).

1b) 2,8-Bis-((E)-styryl)-dibenzofuran

Tetrethylamine hydroxide (13.6 g, 18.4 mmol),tetrakis(triphenylphosphine)palladium(0) (142 mg) andtrans-2-phenylvinylboronic acid (2.3 g, 15.3 mmol) are added to asolution of the product from example 1a) (2.00 g, 6.14 mmol) inN,N′-Dimethylacetamide (DMA) (30 ml). The mixture is then stirred at110° C. for 24 hours. The reaction mixture is cooled to room temperatureand poured into H₂O. A gray crude product is obtained after filtrationand washing with n-hexane. The crude product is purified by silicagelcolumn chromatography with CH₂Cl₂, which result in a white solid (71%yield, mp.: 226° C.).

¹H-NMR (CDCl₃, ppm): 7.26-7.30 (m, 6H), 7.39 (t, 4H), 7.54-7.58 (m, 6H),7.65 (dd, 2H), 8.12 (d, 2H)

Example 2 Synthesis of 1,5-dibenzofuranyl-3,7-di-tert-butylnaphthalene

2a) 1,5-dibromo-3,7-di-tert-butylnaphthalene

Fe (212 mg) and bromine (18.3 g, 0.11 mol) in carbontetrachloride (75ml) are added at 0° C. to a solution of 2,6-di-tert-butylnaphthalene (25g, 0.1 mol) in carbontetrachloride (300 ml). The mixture is then stirredat 0° C. for 3.5 hours. The reaction mixture is poured into H₂O and thenthe organic layer is washed with Na₂S₂O₃ aq. and H₂O. The organic layeris dried over MgSO₄ and concentrated by evaporation. The crude productis then purified by silicagel column chromatography with n-hexane, whichresult in a white solid (31% yield; mp.: 226° C.).

¹H-NMR (CDCl₃, ppm): 1.41 (s, 18H), 7.88 (d, 2H), 8.11 (d, 2H).

2b) 1,5-Dibenzofuranyl-3,7-di-tert-butylnaphthalene

Tetrethylaminehydroxide (3.5 g, 14.2 mmol),tetrakis(triphenylphosphine)palladium(0) (100 mg) and4-denzofuranboronic acid (3 g, 14.0 mmol) are added to a solution of theproduct from example 2a) (1.88 g, 4.72 mmol) in DMA (30 ml). The mixtureis stirred at 110° C. for 1 hour, then cooled to room temperature,whereby a yellow solid product is obtained which is isolated byfiltration and washed with H₂O. The yellow solid is then dissolved inCH₂Cl₂ and dried over MgSO₄. Concentration by evaporation and silicagelcolumn chromatography with ethylacetate/hexane=1/30 as eluent afforded apure yellow solid product (65% yield; mp.: 226° C.).

¹H-NMR (CDCl₃, ppm): 1.98 (s, 18H), 7.38-7.58 (m, 8H), 7.67 (d, 2H),7.77 (d, 2H), 7.82 (d, 2H), 8.08 (dd, 2H), 8.11 (dd, 2H).

The compounds shown below (examples 3-10) are prepared in analoguesmanner using the appropriate educts.

Example Structure Mp. [° C.] 3

247 4

290 5

255 6

7

230 8

9

10

Example 11 Synthesis of 2-Phenanthren-9-yl-8-pyren-1-yl-dibenzofuran11a) 2-Bromodibenzofuran

Bromine (23.8 g, 0.156 mol) in acetic acid (5 g) is added at 50° C. to asolution of dibenzofuran (25 g, 0.149 mol) in acetic acid (230 g). Themixture is then stirred at 50° C. for 4 hours. The reaction mixture iscooled to room temperature and poured into H₂O. The orange solid iswashed with Na₂S₂O₃ aq. and H₂O. The crude product is then purified byrecrystallization from toluene/CH₂Cl₂, wherein the pure product isobtained as a white solid (13% yield).

¹H-NMR (CDCl₃, ppm): 7.59-7.73 (m, 5H), 7.90 (d, 1H), 8.70 (d, 1H)

11b) 2-Bromo-8-iododibenzofuran

2-Bromodibenzofuran (2.5 g, 10.1 mmol), orthoperiodic acid (0.49 g, 2.15mmol), iodine (1.02 g, 4.02 mmol), sulfuric acid, H₂O (2 ml) and aceticacid (10 ml) are put into a reaction vessel and the mixture is stirredat 70° C. for 3 hours. After cooling to room temperature the reactionmixture is poured into water and filtered. The white solid is washed bymethanol and the desired product is obtained (1.92 g, 51%).

¹H-NMR (CDCl₃, ppm): 7.34 (d, 1H), 7.44 (d, 1H), 7.57 (dd, 1H), 7.75(dd, 1H), 8.01 (d, 1H), 8.22 (d, 1H)

11c) 2-Bromo-8-pyren-1-yl-dibenzofuran

20% aq. solution of tetraethylammoninm hydroxide (5.33 g, 7.24 mmol),tetrakis-(triphenylphosphine)palladium(0) (200 mg) and1-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)pyrene (1.74 g, 5.3 mmol)are added to a solution of the product of example 11b) (1.81 g, 4.83mmol) in N,N′-dimethylacetamide (DMA) (70 ml). The mixture is thenstirred at 120° C. for 3 hours. The reaction mixture is cooled down toroom temperature and poured into H₂O. A gray crude product is obtainedafter filtration and washing with n-hexane. The crude product ispurified by silicagel column chromatography with hexane/CH₂Cl₂—, whichresult in a white solid (71% yield).

¹H-NMR (CDCl₃, ppm): 7.53 (d, 1H), 7.61 (dd, 1H), 7.75 (d, 2H),8.01-8.28 (m, 12H)

11d) 2-Phenanthren-9-yl-8-pyren-1-yl-dibenzofuran (A-17) is prepared inanalogy to example 2b) using the compound obtained in step 11c) and9-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)phenanthrene.

¹H-NMR (CDCl₃, ppm): 7.53-7.57 (m, 1H), 7.60-7.70 (m, 4H), 7.74-7.83 (m,4H), 7.90-8.00 (m, 2H), 8.01-8.09 (m, 3H), 8.15 (d, 2H), 8.15-8.26 (m,6H), 8.74 (d, 1H), 8.80 (d, 1H)

The compounds of examples 12 and 13, which are shown below, are preparedin analogues manner to example 11 using the appropriate educts.

Example 12 Diphenyl-[4-(8-pyren-1-yl-dibenzofuran-2-yl)-phenyl]-amine

¹H-NMR (CDCl₃, ppm): 7.00-7.06 (m, 2H), 7.12-7.18 (m, 6H), 7.24-7.28 (m,3H), 7.54-7.58 (d, 2H), 7.64-7.78 (m, 4H), 8.01-8.28 (m, 12H)

Example 13 2-Naphthalen-2-yl-8-pyren-1-yl-dibenzofuran

¹H-NMR (CDCl₃, ppm): 7.46-7.53 (m, 2H), 7.73-7.96 (m, 8H), 8.01-8.15 (m,6H), 8.17-8.29 (m, 5H), 8.32 (d, 1H)

Example 14 9,10-Bis-dibenzofuran-4-yl-2,6-di-tert-butyl-anthracen

Compound B-14 is prepared in analogues manner to example 2 using theappropriate educts.

¹H-NMR (CDCl₃, ppm): 1.15 (s, 18H), 7.35-7.43 (m, 8H), 7.58-7.67 (m,8H), 8.08-8.12 (m, 2H), 8.18 (dd, 2H)

Example 15 Synthesis of4-(2,6-Di-tert-butyl-10-naphthalen-2-yl-anthracen-9-yl)-dibenzofuran15a) 9-Bromo-2,6-di-tert-butyl-anthracene

Bromine (3.02 g, 18.9 mmol) is added at 0° C. to a solution of2,6-di-tert-butylanthracene (5.0 g, 17.2 mol) in carbontetrachloride(200 ml). The mixture is then stirred at 0° C. for 15 hours. Afterallowing to heat up to room temperature, half the amount of solvent isevaporated and the resulting mixture is poured into methanol. Theprecipitate is collected by filtration, recrystallized fromn-hexane/methanol and the desired product is obtained as a white solid(1.13 g).

¹H-NMR (CDCl₃, ppm): 1.47 (s, 9H), 1.48 (s, 9H), 7.58 (dd, 1H), 7.67(dd, 1H), 7.85 (d, 1H), 7.91 (d, 1H), 8.33 (s, 1H), 8.38 (d, 1H), 8.43(d, 1H)

15b) 9-Bromo-2,6-di-tert-butyl-10-iodo-anthracene

Iodination is done in the same manner as described in example 11b) usingthe compound obtained in example 15a) as starting material.

¹H-NMR (CDCl₃, ppm): 1.48 (2s, 18H), 7.65-7.72 (m, 2H), 8.42-8.52 (m,4H)

15c) 4-(10-Bromo-2,6-di-tert-butyl-anthracen-9-yl)-dibenzofuran

The compound shown above is prepared in the same manner as described inexample 11c) using the compound obtained in example 15b) and1-dibenzofuranylboronic acid as starting materials.

¹H-NMR (CDCl₃, ppm): 1.18 (s, 9H), 1.46 (s, 9H), 7.29-7.33 (m, 1H),7.35-7.42 (m, 3H), 7.48-7.59 (m, 4H), 7.68 (dd, 1H), 8.07 (m, 1H), 8.15(dd, 1H), 8.53 (d, 1H), 8.58 (d, 1H)

15d)4-(2,6-Di-tert-butyl-10-naphthalen-2-yl-anthracen-9-yl)-dibenzofuran(A-35) is prepared in the same manner as described in example 2b) usingthe compound obtained in step 15c) and2-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) naphthalene as startingmaterials.

¹H-NMR (CDCl₃, ppm): 1.16 (s, 9H), 1.21 (s, 9H), 7.35-7.42 (m, 5H),7.55-7.73 (m, 9H), 7.92-7.97 (m, 1H), 8.01-8.11 (m, 4H), 8.16-8.19 (m,1H)

Example 164-(2,6-Di-tert-butyl-10-pyren-1-yl-anthracen-9-yl)-dibenzofuran

Example 15 is repeated except using1-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)pyrene in the last step.

¹H-NMR (CDCl₃, ppm): 1.05 (s, 9H), 1.14 (s, 9H), 7.24-8.44 (m, 22H)

Example 17 2,6-Di-pyren-1-yl-dibenzofuran 17a)6-Bromo-2-iodo-dibenzofuran

6-Bromo-2-iodo-dibenzofuran is prepared in the same manner as describedin example 11b), except using 4-bromodibenzofurane as a startingmaterial.

¹H-NMR (CDCl₃, ppm): 7.22-7.27 (t, 1H), 7.42-7.45 (d, 1H), 7.62-7.66(dd, 1H), 7.75-7.79 (dd, 1H), 7.82-7.85 (dd, 1H), 8.26 (d, 1H)

17b) 6-Bromo-2-pyren-1-yl-dibenzofuran

6-Bromo-2-pyren-1-yl-dibenzofuran is prepared in the same manner asdescribed in example 11c), except using 6-Bromo-2-iodo-dibenzofuran as astarting material.

¹H-NMR (CDCl₃, ppm): 7.24-7.28 (t, 1H), 7.65-7.68 (dd, 1H), 7.74-7.77(dd, 1H), 7.82-7.85 (d, 1H), 7.91-7.94 (dd, 1H), 8.01-8.06 (m, 3H),8.12-8.27 (m, 7H)

17c) 2,6-Di-pyren-1-yl-dibenzofuran (A-58)

A-58 is prepared in analogy to A-17 using the appropriate educts.

¹H-NMR (CDCl₃, ppm): 7.58-7.62 (m, 2H), 7.67-7.74 (m, 2H), 8.02-8.10 (m,6H), 8.13-8.30 (m, 13H), 8.35-8.38 (d, 1H)

Example 18 6-Phenanthren-9-yl-2-pyren-1-yl-dibenzofuran

A-59 is prepared in analogy to A-58 using the appropriate educts.

¹H-NMR (CDCl₃, ppm): 7.52-7.61 (m, 3H), 7.63-7.80 (m, 6H), 7.95-8.28 (m,13H), 8.80-8.83 (d, 1H), 8.84-8.88 (d, 1H)

Example 19

A-60 is prepared in analogy to A-17 using the appropriate educts.

¹H-NMR (CDCl₃, ppm): 6.64-6.89 (m, 5H), 7.04-7.46 (m, 11H), 8.0-8.26 (m,14H)

Example 20

A-61 is prepared in analogy to A-58 using the appropriate educts.

¹H-NMR (CDCl₃, ppm): 6.62-6.86 (m, 5H), 7.02-7.14 (m, 5H), 7.30-7.40 (m,5H), 7.58 (s, 1H), 7.66-8.26 (m, 14H)

Application Examples Application Example 1

Compounds A-1, B-1, C-1, C-2, A-9, A-10 and A-7, respectively aredeposited under vacuum on a glass plate in a thickness of 60 nm.Fluorescence spectra of the deposited films are measured by fluorescencespectrophotometer (F-4500, HITACHI). The emission λ_(max) is shownbelow.

Compound Emission λ_(max) [nm] A-1 421 B-1 383 C-1 420 C-2 387 A-9 364A-10 474 A-7 454

Application Example 2

The following device structure is prepared: ITO/CuPC/TCTA/CompoundB-1/TPBl/LiF/Al where ITO is indium tin oxide, CuPC is copperphthalocyanine, TCTA is 4,4′,4″-tri-(N-carbazoyl)triphenylamine and TPBlis 1,3,5-tris-(N-phenyl-benzimidazol-2-yl)benzene. Using this devicestructure, a brightness of 50 cd/m² is observed at 100 mA/cm².

Application Example 3

The following device structure is prepared: ITO/CuPC/TCTA/CompoundB-1+Compound G-1 (1.1% by weight)/TPBl/LiF/Al. Using this devicestructure, a brightness of 500 cd/m² is observed at 100 mA/cm².

Compound G-1 (WO03105538) Application Example 4

The following device structure is prepared: ITO/CuPC/TCTA/CompoundC-2/TPBl/LiF/Al. Using this device structure, a brightness of 120 cd/m²is observed at 100 mA/cm².

Application Example 5

The following device structure is prepared: ITO/CuPC/TCTA/CompoundC-2+Compound G-1 (1.9% by weight)/TPBl/LiF/Al. Using this devicestructure, a brightness of 70 cd/m² is observed at 100 mA/cm².

Application Example 6

The following device structure is prepared: ITO/CuPC/NPD/CompoundB-1/TPBl/LiF/Al where NPD isN,N′-Di(naphthalene-1-yl)-N,N′-diphenyl-benzidine. Using this devicestructure, a brightness of 370 cd/m² is observed at 100 mA/cm2.

Application Example 7

The following device structure is prepared: ITO/CuPC/NPD/CompoundB-1+TBPe (1.4%)/TPBl/LiF/Al where TPBe is2,5,8,11-tetra-t-butylperylene. Using this device structure, abrightness of 680 cd/m² is observed at 88 mA/cm².

Application Example 8

The following device structure is prepared: ITO/CuPC/NPD/CompoundA-10/TPBl/LiF/Al. Using this device structure, a brightness of 3,800cd/m² is observed at 111 mA/cm2.

Application Example 9

The following device structure is prepared: ITO/CuPC/NPD/CompoundA-10+TBPe (1.5%)/TPBl/LiF/Al. Using this device structure, a brightnessof 2,030 cd/m² is observed at 90 mA/cm².

Application Examples 10 to 21

The following device structure is prepared: ITO/CuPC/NPD/Emitting layer(dibenzofuran of the present invention as a host+TBPe as aguest)/TPBl/LiF/Al. Using this device structure, bright blue EL emissionis observed. The EL properties of the devices are summarized in Table 1.

TABLE 1 EL properties obtained in application examples 10 TO 21 Guest(TBPe) Current Application Concentration Brightness Efficiency VoltageEmission Example Host (%) (cd/m²) (cd/A) (V) peak (nm) 10 C-2 2.4 1582.5 10 467, 493 11 C-1 1.7 99 1.1 7 462, 489 12 A-17 — 133 3.3 7.4 46513 A-17 1.6 79 4.0 7.2 467, 492 14 B-14 — 86 2.2 7.6 459 15 B-14 1.8 974.9 7.1 462, 490 16 A-57 — 108 2.7 8.3 460 17 A-57 1.6 95 2.4 8.1 464,489 18 A-43 — 120 3.0 5.1 461 19 A-43 1.5 96 4.8 4.7 465, 491 20 A-50 —139 3.5 6.8 466 21 A-50 1.5 88 4.4 6.4 467, 492 22 A-35 — 86 4.3 7.6 46723 A-35 1.3 98 4.9 7.4 461, 488 24 A-58 — 104 5.2 6.4 465 25 A-58 2.1 894.4 6.7 467, 490

Application Example 26

The following device structure is prepared: ITO/CuPC/NPD/Emitting layer(dibenzofuran of the present invention as a host+dibenzofuran of thepresent invention as a guest)/TPBl/LiF/Al. Using this device structure,bright blue EL emission is observed. The EL properties of the device issummarized in Table 2.

TABLE 2 EL properties obtained in application example 26 CurrentApplication Brightness Efficiency Voltage Emission Example Host Guest(cd/m²) (cd/A) (V) Peak (nm) 26 A-17 B-14 83 2.1 7.5 462 (5.1%)

1. A compound of the formula

wherein R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸, R⁹¹, R⁹², R⁹³, R⁹⁴, R⁹⁵,R⁹⁶, R⁹⁷, R^(91′), R^(92′), R^(93′), R^(94′), R^(95′), R^(96′) andR^(97′) are independently of each other H, —OR²⁰¹, —SR²⁰², NR²⁰³R²⁰⁴,C₁-C₂₄alkyl; C₁-C₂₄alkyl, which is substituted by E and/or interruptedby D; C₂-C₁₈alkenyl, C₂-C₁₈alkenyl, which is substituted by E,C₃-C₈cycloalkyl, C₃-C₈cycloalkyl, which is substituted by G, aryl, aryl,which is substituted by G, heteroaryl, or heteroaryl, which issubstituted by G, silyl,

SiR⁶²R⁶³R⁶⁴, —CN, cyclic ether, —B(OR⁶⁵)₂ or halogen, or R⁸¹ and R⁸²,R¹² and R⁸³, R⁸³ and R⁸⁴, R⁸⁵ and R⁸⁶, R⁸⁶ and R⁸⁷, R⁸⁷ and R⁸⁸, R⁹⁷ andR⁹⁶, R⁹⁶ and R⁹⁵, R⁹⁵ and R⁹⁴, R^(97′) and R^(96′), R^(96′) and R^(95′),R^(95′) and R^(94′), and/or two of the groups R⁹¹, R⁹² and R⁹³ orR^(91′), R^(92′) and R^(93′), which are in neighbourhood to each other,together form a group

wherein A⁴¹, A⁴², A⁴³, A⁴⁴, A⁴⁵, A⁴⁶ and A⁴⁷ are independently of eachother H, halogen, hydroxy, C₁-C₂₄alkyl, C₁-C₂₄alkyl which is substitutedby E and/or interrupted by D, C₁-C₂₄ perfluoroalkyl, C₅-C₁₂cycloalkyl,C₅-C₁₂cycloalkyl which is substituted by G and/or interrupted by S—,—O—, or —NR⁵—, C₅-C₁₂cycloalkoxy, C₅-C₁₂cycloalkoxy which is substitutedby E, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,C₂-C₂₄alkenyl, C₂-C₂₄alkynyl, C₁-C₂₄alkoxy, C₁-C₂₄alkoxy which issubstituted by E and/or interrupted by D, C₇-C₂₅aralkyl, C₇-C₂₅aralkyl,which is substituted by G, C₇-C₂₅aralkoxy, C₇-C₂₅aralkoxy which issubstituted by E, or —CO—R⁸, M is a single (direct) bond, —CO—, —COO—;—S—; —SO—; —SO₂—; —O—; C₁-C₁₂alkylene, C₂-C₁₂alkenylene, orC₂-C₁₂alkinylene, which are optionally interrupted by one or more —O—,or —S—; or a group [M¹]_(n), wherein n is an integer 1 to 20, M¹ isarylene, or heteroarylene, which is optionally substituted by G, D is—CO—, —COO—, —OCOO—, —S—, —SO—, —SO₂—, —O—, —NR⁵—, —SiR⁶¹R⁶²—, —POR⁵—,—CR⁶³═CR⁶⁴—, or —C≡C—; E is halogen, C₆-C₁₄aryl, which may besubstituted by —OR⁵, —SR⁵, —NR⁵R⁶,

SiR⁶²R⁶³R⁶⁴, wherein R⁶², R⁶³ and R⁶⁴ are independently of each other aC₁-C₈alkyl group, a C₆-C₂₄aryl group or a C₇-C₁₂aralkylgroup, —CN,cyclic ether or —B(OR⁶⁵)₂, wherein R⁶⁵ is hydrogen, C₁-C₂₄alkyl,C₃-C₈cycloalkyl, C₇-C₂₄aralkyl, C₂-C₁₈alkenyl, C₂-C₂₄alkynyl, hydroxy,mercapto, C₁-C₂₄alkoxy, C₁-C₂₄alkylthio, C₆-C₃₀aryl, C₂-C₃₀heteroaryl,halogen, haloalkane, silyl, siloxanyl, or an alicyclic ring formed withadjacent substituents R⁶⁵; —OR⁵, —SR⁵, —NR⁵R⁶, —COR⁸, —COOR⁷, —CONR⁵R⁶,—CN, halogen, silyl, C₁-C₁₈alkyl, or heteroaryl, G is E, or C₁-C₁₈alkyl,wherein R⁵ and R⁶ are independently of each other H, C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy, or silyl;C₁-C₁₈alkyl or C₁-C₁₈alkyl which is interrupted by —O—; or R⁵ and R⁶together form a five or six membered ring, R⁷ is H, C₆-C₁₈aryl,C₇-C₁₂alkylaryl, which are optionally substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—;R⁸ is C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl, C₇-C₁₂alkylaryl, or C₁-C₁₈alkyl which isinterrupted by —O—; R⁶¹ and R⁶² are independently of each otherC₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl,C₁-C₁₈alkoxy; or C₁-C₁₈alkyl which is interrupted by —O—, and R⁶³ andR⁶⁴ are independently of each other H, C₆-C₁₈aryl; C₆-C₁₈aryl which issubstituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy; or C₁-C₁₈alkyl which isinterrupted by —O—; with the proviso that at least one of R⁸¹, R⁸², R⁸³,R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷ and R⁸⁸ is different from H, —OR²⁰¹, —SR²⁰² andC₁-C₂₄alkyl wherein R²⁰¹ is hydrogen, C₁-C₂₄alkyl, C₁-C₂₄alkyl, which issubstituted by E and/or interrupted by D; C₂-C₁₂alkenyl, C₃-C₆alkenoyl,C₃-C₈cycloalkyl, or benzoyl, each of which may optionally be substitutedby one or more groups C₁-C₆alkyl, halogen, —OH and/or C₁-C₄alkoxy:C₆-C₁₄aryl, especially phenyl, naphthyl, phenanthryl, anthranyl, orpyrenyl, each of which may optionally be substituted by halogen, —OH,C₁-C₁₂alkyl, C₁-C₁₂alkoxy, phenoxy, C₁-C₁₂alkylsulfanyl, phenylsulfanyl,—N(C₁-C₁₂alkyl)₂ and/or diphenylamino: R²⁰² is C₁-C₂₄alkyl, C₁-C₂₄alkyl,which is substituted by E and/or interrupted by D; C₂-C₁₂alkenyl,C₁-C₈alkanoyl, C₂-C₁₂alkenyl, C₃-C₆alkenoyl; C₃-C₈cycloalkyl, orbenzoyl, each of which may optionally be substituted by one or moregroups C₁-C₆alkyl, halogen, —OH, C₁-C₄alkoxy or C₁-C₄alkylsulfanyl;C₆-C₁₄aryl, especially phenyl, naphthyl, phenanthryl, anthranyl, orpyrenyl, each of which may optionally be substituted by halogen,C₁-C₁₂alkyl, C₁-C₁₂alkoxy, phenyl-C₁-C₃alkyloxy, phenoxy,C₁-C₁₂alkylsulfanyl, phenylsulfanyl, —N(C₁-C₁₂alkyl)₂, diphenylamino,—(CO)O(C₁-C₈alkyl), —(CO)—C₁-C₈alkyl, or (CO)N(C₁-C₈alkyl); and thefurther proviso that the following compounds are excluded:


2. The compound of formula II according to claim 1, wherein M is asingle bond,

n1, n2, n3, n4, n5, n6 and n7 are integers of 1 to 10, A⁶ and A⁷ areindependently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E′ and/or interrupted by D′, C₆-C₂₄aryl, C₆-C₂₄aryl whichis substituted by G′, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which issubstituted by G′, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E′ and/or interrupted by D′,C₇-C₂₅aralkyl, or —CO-A²⁸, A⁸ is C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E′ and/or interrupted by D′, C₆-C₂₄ aryl, orC₇-C₂₅aralkyl, A⁹ and A¹⁰ are independently of each other C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E′ and/or interrupted by D′,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G′, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G′, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E′and/or interrupted by D′, or C₇-C₂₅aralkyl, or A⁹ and A¹⁰ form a ring,which can optionally be substituted by one or more C₁-C₁₈ alkyl groups;A¹⁴ and A¹⁵ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is substituted by E′ and/or interrupted by D′, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G′, C₂-C₂₀heteroaryl, orC₂-C₂₀heteroaryl which is substituted by G′, D′ is —CO—; —COO—; —S—;—SO—; —SO₂—; —O—; —NA²⁵-; —SiA³⁰A³¹-; —POA³²-; —CA²³=CA²⁴-; or —C≡C—;and E′ is —OA²⁹; —SA²⁹; —NA²⁵A²⁶; —COA²⁸; —COOA²⁷; —CONA²⁵A²⁶; —CN;—OCOOA²⁷; or halogen; G′ is E′, or C₁-C₁₈alkyl; wherein A²³, A²⁴, A²⁵and A²⁶ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈aryl whichis substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl, orC₁-C₁₈alkyl which is interrupted by —O—; or A²⁵ and A²⁶ together form afive or six membered ring, A²⁷ and A²⁸ are independently of each otherH; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is interrupted by —O—,A²⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl,or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by—O—, A³⁰ and A³¹ are independently of each other C₁-C₁₈alkyl,C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, and A³²is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted byC₁-C₁₈alkyl.
 3. The compound of formula I according to claim 1, whereinat least one of the groups R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸, R⁸⁹,R⁹², R⁹³, R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷, R^(91′), R^(92′), R^(93′), R^(94′),R^(95′), R^(96′) and R^(97′) is a group

wherein A^(14′) and A^(15′) are independently of each other H,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,or C₂-C₂₀heteroaryl which is substituted by G, and A^(16′) is H,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,or C₂-C₂₀heteroaryl which is substituted by G; or a polycyclic arylgroup, which can optionally be substituted by G.
 4. The compound offormula I according to claim 1, wherein at least one of the groups R⁸¹,R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸, R⁹¹, R⁹², R⁹³, R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷,R^(91′), R^(92′), R^(93′), R^(94′), R^(95′), R^(96′) and R^(97′) is agroup of the formula —(W¹)_(a)—(W²)_(b)—W³, wherein a and b are 0, or 1,W¹ and W² are independently of each other a group of formula

W³ is a group of formula

or

R¹¹, R^(11′), R¹², R^(12′), R¹³, R^(13′), R¹⁵, R^(15′), R¹⁶, R^(16′),R¹⁷, R^(17′), R⁴¹, R^(41′), R⁴², R^(42′), R⁴⁴, R^(44′), R⁴⁵, R^(45′),R⁴⁶R^(46′), R⁴⁷ and R^(47′) are independently of each other H, E, silyl,C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by G; C₁-C₁₈alkyl;C₁-C₁₈alkyl which is substituted by E and/or interrupted by D;C₁-C₁₈alkoxy; or C₁-C₁₈alkoxy which is substituted by E and/orinterrupted by D; C₇-C₁₈aralkyl; or C₇-C₁₈aralkyl which is substitutedby G; R¹⁴ is H, C₁-C₁₈alkyl; silyl, or C₁-C₁₈alkyl which is substitutedby E and/or interrupted by D; C₁-C₁₈alkoxy; or C₁-C₁₈alkoxy which issubstituted by E and/or interrupted by D;

R¹⁸ and R¹⁹ are independently of each other C₁-C₁₈alkyl; C₁-C₁₈alkoxy,C₆-C₁₈aryl; C₇-C₁₈aralkyl; or R¹⁸ and R¹⁹ together form a ringespecially a five- or six-membered ring, which can optionally besubstituted by C₁-C₈alkyl, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶ and R²⁷ areindependently of each other H, E, C₁-C₁₈alkyl; C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D; C₇-C₁₈aralkyl; C₇-C₁₈aralkylwhich is substituted by G; or W³ is a group of formula

R³¹⁵ and R³¹⁶ are independently of each other a hydrogen atom, aC₁-C₁₈alkyl group, a C₁-C₁₈alkoxy group, a group of formula

wherein R³¹⁸, R³¹⁹ and R³²⁰ independently from each other stand forhydrogen, C₁-C₈-alkyl, C₁-C₈-alkoxy, or phenyl, and R³¹⁷ stands for is ahydrogen atom, a C₁-C₂₅alkyl group, which may be interrupted by —O—, acycloalkyl group, a C₇-C₁₈aralkyl group, a C₆-C₁₈aryl group, or aheterocyclic group, which may be substituted by G; wherein D is —CO—,—COO—, —OCOO—, —S—, —SO—, —SO₂—, —O—, —NR⁵—, SiR⁶¹R⁶²—, —POR⁵—,—CR⁶³═CR⁶⁴—, or —C≡C—; E is —OR⁵, —SR⁵, —NR⁵R⁶, —COR⁸, —COOR⁷, —OCOOR⁷,—CONR⁵R⁶, —CN, or halogen; G is E, or C₁-C₁₈alkyl; wherein R⁵ and R⁶ areindependently of each other C₆-C₁₈aryl; C₆-C₁₈aryl which is substitutedby C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl, or C₁-C₁₈alkyl which isinterrupted by —O—; or R⁵ and R⁶ together form a five or six memberedring, R⁷ is C₇-C₁₂alkylaryl; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which isinterrupted by —O—; R⁸ is C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; C₇-C₁₂alkylaryl, orC₁-C₁₈alkyl which is interrupted by —O—; R⁶¹ and R⁶² are independentlyof each other C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₁₈alkyl which is interrupted by—O—, and R⁶³ and R⁶⁴ are independently of each other H, C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy; orC₁-C₁₈alkyl which is interrupted by —O—; or W³ is a group of formula—NR⁷⁰R⁷¹, wherein R⁷⁰ and R⁷¹ are independently of each other a group offormula

wherein R⁷², R⁷³ and R⁷⁴ are independently of each other hydrogen,C₁-C₈alkyl, a hydroxyl group, a mercapto group, C₁-C₈alkoxy,C₁-C₈alkylthio, halogen, halo-C₁-C₈alkyl, a cyano group, an aldehydegroup, a ketone group, a carboxyl group, an ester group, a carbamoylgroup, an amino group, a nitro group, a silyl group or a siloxanylgroup, or R⁷⁰ and R⁷¹ together with the nitrogen atom to which they arebonded form a five or six membered heterocyclic ring, which can becondensed by one or two optionally substituted phenyl groups.
 5. Thecompound according to claim 1, of the formula:


6. The compound of formula I according to claim 4, wherein W³ is a groupof formula —NR⁷⁰R⁷¹, wherein R⁷⁰ and R⁷¹ are independently of each othera group of formula

wherein R⁷², R⁷³ and R⁷⁴ are independently of each other hydrogen,C₁-C₈alkyl, a hydroxyl group, a mercapto group, C₁-C₈alkoxy,C₁-C₈alkylthio, halogen, halo-C₁-C₈alkyl, a cyano group, an aldehydegroup, a ketone group, a carboxyl group, an ester group, a carbamoylgroup, an amino group, a nitro group, a silyl group or a siloxanylgroup, or R⁷⁰ and R⁷¹ together with the nitrogen atom to which they arebonded form a five or six membered heterocyclic ring, which can becondensed by one or two optionally substituted phenyl groups.
 7. Thecompound according to claim 6:


8. A composition comprising a compound according to claim
 1. 9. Anelectroluminescent device, comprising a compound according to claim 1.10. Electrophotographic photoreceptors, photoelectric converters, solarcells, image sensors, dye lasers and electroluminescent devicescomprising a compound according to claim
 1. 11. A compound according toclaim 1 wherein when any of R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸, R⁹¹,R⁹², R⁹³, R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷, R^(91′), R^(92′), R^(93′), R^(94′),R^(95′), R^(96′) or R^(97′) is halogen, the halogen is fluorine; when Mis a group [M¹]_(n), M¹ is naphthylene, biphenylene, styrylene,anthrylene, or pyrenylene, which are optionally substituted byC₁-C₁₂alkyl, halogen, —OR²⁰¹, —SR²⁰² and/or —NR²⁰³R²⁰⁴, wherein R²⁰¹ ishydrogen, C₁-C₂₄alkyl, C₁-C₂₄alkyl, which is substituted by E and/orinterrupted by D; C₂-C₁₂alkenyl, C₃-C₆alkenoyl, C₃-C₈cycloalkyl, orbenzoyl, each of which may optionally be substituted by one or moregroups C₁-C₆alkyl, halogen, —OH and/or C₁-C₄alkoxy; C₆-C₁₄aryl,especially phenyl, naphthyl, phenanthryl, anthranyl, or pyrenyl, each ofwhich may optionally be substituted by halogen, —OH, C₁-C₁₂alkyl,C₁-C₁₂alkoxy, phenoxy, C₁-C₁₂alkylsulfanyl, phenylsulfanyl,—N(C₁-C₁₂alkyl)₂ and/or diphenylamino; R²⁰² is C₁-C₂₄alkyl, C₁-C₂₄alkyl,which is substituted by E and/or interrupted by D; C₂-C₁₂alkenyl,C₁-C₈alkanoyl, C₂-C₁₂alkenyl, C₃-C₆alkenoyl; C₃-C₈cycloalkyl, orbenzoyl, each of which may optionally be substituted by one or moregroups C₁-C₆alkyl, halogen, —OH, C₁-C₄alkoxy or C₁-C₄alkylsulfanyl;C₆-C₁₄aryl, especially phenyl, naphthyl, phenanthryl, anthranyl, orpyrenyl, each of which may optionally be substituted by halogen,C₁-C₁₂alkyl, C₁-C₁₂alkoxy, phenyl-C₁-C₃alkyloxy, phenoxy,C₁-C₁₂alkylsulfanyl, phenylsulfanyl, —N(C₁-C₁₂alkyl)₂, diphenylamino,—(CO)O(C₁-C₈alkyl), —(CO)—C₁-C₈alkyl, or (CO)N(C₁-C₈alkyl)₂; R²⁰³ andR²⁰⁴ are independently of each other hydrogen, C₁-C₂₄alkyl, C₁-C₂₄alkyl,which is substituted by E and/or interrupted by D; C₂-C₅alkenyl,C₃-C₈cycloalkyl, or benzoyl, each of which may optionally be substitutedby one or more groups C₁-C₆alkyl, halogen, —OH, or C₁-C₄alkoxy;phenyl-C₁-C₃alkyl, C₁-C₈alkanoyl, C₃-C₁₂alkenoyl, C₆-C₁₄aryl, especiallyphenyl naphthyl, phenanthryl, anthranyl, or pyrenyl, each of which isoptionally substituted by C₁-C₁₂alkyl, benzoyl or C₁-C₁₂alkoxy; or R²⁰³and R²⁰⁴ together are C₂-C₈alkylene, or branched C₂-C₈alkyleneoptionally interrupted by —O—, —S—, or —NR²⁰⁵— and/or optionallysubstituted by hydroxyl, C₁-C₄alkoxy, C₂-C₄alkanoyloxy, or benzoyloxy,wherein the ring formed by R²⁰³ and R²⁰⁴ can optionally be condensed oneor two times by phenyl which can be substituted one to three times withC₁-C₈-alkyl, C₁-C₈-alkoxy, halogen, or cyano; R²⁰⁵ is hydrogen,C₁-C₂₄alkyl, C₁-C₂₄alkyl, which is substituted by E and/or interruptedby D; C₂-C₅alkenyl, C₃-C₈cycloalkyl, phenyl-C₁-C₃alkyl, C₁-C₈alkanoyl,C₃-C₁₂alkenoyl, C₆-C₁₄aryl, especially benzoyl; phenyl, naphthyl,phenanthryl, anthranyl, or pyrenyl, each of which is optionallysubstituted by C₁-C₁₂alkyl, benzoyl, or C₁-C₁₂alkoxy; When E isC₆-C₁₄aryl, the aryl is phenyl, naphthyl, phenanthryl, anthranyl, orpyrenyl, which may be substituted as described; and when R⁵ and R⁶together form a five or six membered ring, the ring is selected from


12. A compound according to claim 2, wherein when M is of the formula

it a group of the formula

when M is of the formula

it a group of the formula

when M is of the formula

it a group of the formula

when M is of the formula

it a group of the formula

when M is of the formula

it a group of the formula

when M is of the formula

it a group of the formula

wherein when A⁹ and A¹⁰ form a ring which can optionally be substitutedby one or more C₁-C₁₈ alkyl groups, it is a five- or six-membered ring;and when A²⁵ and A²⁶ together form a ring, it is selected from


13. The compound according to claim 3, wherein the polycyclic aryl groupis selected from pentalenyl, indenyl, azulenyl, naphthyl, biphenylenyl,as-indacenyl, s-indacenyl, acenaphthylenyl, fluorenyl, phenanthryl,anthracenyl, fluoranthenyl, acephenanthrylenyl, aceanthrylenyl,triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, picenyl, perylenyl,pentacenyl, pentaphenyl, hexacenyl, and hexaphenyl, any of which canoptionally be substituted by G.
 14. The compound of formula I accordingto claim 4, wherein when R⁷⁰ and R⁷¹ together with the nitrogen atom towhich they are bonded form a five or six membered heterocyclic ringwhich can be condensed by one or two optionally substituted phenylgroups, the ring is selected from

wherein R²¹⁶ and R²¹⁷ independently from each other stands for hydrogen,C₁-C₈alkyl, C₁-C₈alkoxy, or phenyl, and X¹ stands for hydrogen, orC₁-C₈alkyl; R⁷⁵, R⁷⁶, R⁷⁷ and R⁷⁸ are independently of each other H, E,C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by E; C₁-C₁₈alkyl;C₁-C₁₈alkyl which is substituted by G and/or interrupted by D;C₇-C₁₈aralkyl; or C₇-C₁₈aralkyl which is substituted by E.
 15. Thecompound of formula I according to claim 6, wherein when R⁷⁰ and R⁷¹together with the nitrogen atom to which they are bonded form a five orsix membered heterocyclic ring which can be condensed by one or twooptionally substituted phenyl groups, the ring is selected from

wherein R²¹⁶ and R²¹⁷ independently from each other stands for hydrogen,C₁-C₈alkyl, C₁-C₈alkoxy, or phenyl, and X¹ stands for hydrogen, orC₁-C₈alkyl; R⁷⁵, R⁷⁶, R⁷⁷ and R⁷⁸ are independently of each other H, E,C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by E; C₁-C₁₈alkyl;C₁-C₁₈alkyl which is substituted by G and/or interrupted by D;C₇-C₁₈aralkyl; or C₇-C₁₈aralkyl which is substituted by E.
 16. Thecompound of formula I according to claim 6, wherein at least two of thesubstituents R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸, R⁹¹, R⁹², R⁹³, R⁹⁴,R⁹⁵, R⁹⁶, R⁹⁷, R^(91′), R^(92′), R^(93′), R^(94′), R^(95′), R^(96′) andR^(97′) are independently of each other a group of the formula—W¹—(W²)_(b)—W³.
 17. The compound of formula I according to claim 15,wherein at least two of the substituents R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶,R⁸⁷, R⁸⁸, R⁹¹, R⁹², R⁹³, R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷, R^(91′), R^(92′), R^(93′),R^(94′), R^(95′), R^(96′) and R^(97′) are independently of each other agroup of the formula —W¹—(W²)_(b)—W³.